WO2004106311A2 - Triazines d'aminoaryle - Google Patents

Triazines d'aminoaryle Download PDF

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Publication number
WO2004106311A2
WO2004106311A2 PCT/EP2004/050818 EP2004050818W WO2004106311A2 WO 2004106311 A2 WO2004106311 A2 WO 2004106311A2 EP 2004050818 W EP2004050818 W EP 2004050818W WO 2004106311 A2 WO2004106311 A2 WO 2004106311A2
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Prior art keywords
alkyl
phenyl
cycloalkyl
alkenyl
substituted
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PCT/EP2004/050818
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English (en)
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WO2004106311A3 (fr
Inventor
Thomas Schäfer
Frédérique Wendeborn
Michèle Gerster
Pascal Hayoz
Beat Schmidhalter
Jean-Luc Budry
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Ciba Specialty Chemicals Holding Inc.
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Priority to EP04733351A priority Critical patent/EP1641768A2/fr
Priority to US10/558,317 priority patent/US20060252857A1/en
Priority to JP2006530199A priority patent/JP2007508275A/ja
Publication of WO2004106311A2 publication Critical patent/WO2004106311A2/fr
Publication of WO2004106311A3 publication Critical patent/WO2004106311A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/22—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to two ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms

Definitions

  • the invention relates to a novel process for the preparation of aminoaryl triazines, to an optical recording medium containing an aminoaryl triazine and to some novel light stabilizers of the hydroxyphenyl-s-triazine class whose chromophor contains an amino or amido group, obtainable by this process, further to the use of these compounds for stabilizing or protecting organic material or for protecting hair or skin, especially for the protection of plastics, coating materials, cosmetic preparations, sun screen lotions or reprographic or photographic material, from damage by light, oxygen and/or heat, and to correspondingly stabilized organic material.
  • triphenyl-s-triazine UV absorbers are an important class (see e.g. US-A-3 118 887, US-A-4 619 956, WO-96/28431). Some compounds of this class containing amino groups on a phenyl ring are recommended in DE-A-19536376, US-5780214, JP-A-11- 174638, JP-A-11-160840. Certain aminoaryl triazines have been recommended as a dye for optical information recording materials (JP-A-2001-277720; JP-A-2002- 160452). The preparation of some aminophenyl triazines is described in WO 97/36880 via build-up of the triazine core from multiple substituted phenyls.
  • present invention pertains to a process for preparing a compound or mixture of compounds conforming to the formula I'
  • a and A' independently are H, C C ⁇ 8 alkyl; C 5 -C 12 cycloalkyl; C 2 -C 18 alkenyl; C 2 -C 18 alkynyl;
  • R' ⁇ is H; CrC 20 alkyl; C 5 -C ⁇ 2 cycloal yl; C 3 -C ⁇ 8 alkenyl; phenyl; CrC 18 alkyl which is substituted by phenyl, vinylphenyl, C 5 -C ⁇ 2 cycloalkyl, OH, CrC ⁇ 8 alkoxy, C 5 -C ⁇ 2 cycloalkoxy, C 3 - C ⁇ 8 alkenyloxy, halogen, -COOH, -COOR ⁇ -O-CO-R 5 , -O-CO-O-R 6j -CO-NH 2l -CO-NHR 7 , - CO-N(R 7 )(R 8 ), CN, NH 2 , NHR 7 , -N(R 7 )(R 8 ), -NH-CO-R 5) phenoxy, CrC 18 alkyl-phenoxy, phenyl-C ⁇ -C 4 -alkoxy, C 6 -C
  • R' 2 , R' 3 are independently from each other, hydrogen; C C 2 oalkyl; C 2 -C ⁇ 8 alkenyl; C - C 12 cycloalkyl; OH; NH 2 ; OR ⁇ 0 ; NHR 10 ; C C 18 alkyl substituted with phenyl, vinylphenyl, OH, CrC- alkoxy, C 5 -C ⁇ 2 cycloalkoxy, C 3 -C ⁇ 8 alkenyloxy, C C ⁇ 8 alkylthio, phenylthio, phenylthio substituted by C C 18 alkyl, phenyl-C C 4 -alkylthio, -COOH, -CO-NH 2l -CO-NHR 7) -CO- N(R 7 )(R 8 ), NH 2j NHR 7 , -N(R 7 )(R 8 ), -NH-CO-R 5 , phenoxy, phenoxy substituted by C ⁇ -C
  • * is C C ⁇ 8 alkyl; C 3 -C ⁇ 8 alkenyl; phenyl; Cy-Cnphenylalkyl; C 5 -C ⁇ 2 cycloalkyl; C 3 -C5oalkyl, which is interrupted by -O-, -NH-, -NR7-, -S-, and which can be substituted by OH, phenoxy or C 7 -C ⁇ 8 alkyl phenoxy; or is C 2 -C ⁇ 2 hydroxyalkyl;
  • R 5 is C C 18 alkyl; C C ⁇ 8 alkyl substituted by COOH, COOR 4 ; C 2 -C 18 alkenyl; C 2 -C ⁇ 8 alkenyl substituted by COOH or COOR 4 ; C 5 -C ⁇ 2 cycloalkyl; phenyl; C 7 -Cnphenylalkyl; C 7 - C 11 alkyl phenyl; C 6 -C ⁇ 5 bicycloalkyl; C 6 -C ⁇ 5 bicycloalkenyl; C 6 -C 5 tricycloalkyl;
  • R 6 is CrC 18 alkyl; C 3 -C ⁇ 8 alkenyl; phenyl; C 7 -Cnphenylalkyl; C 5 -C ⁇ 2 cycloalkyl; R' 6 is H; C ⁇ -C ⁇ 8 alkyl; C -C ⁇ 8 alkenyl; phenyl; C -Cnphenylalkyl; C 5 -C ⁇ 2 cycloalkyl;
  • R 7 and R 8 are independently phenyl; d-C ⁇ alkyl; C 7 -C ⁇ 3 aralkyl; C 7 -d 3 alkylaryl; C 3 - C 2 alkoxyalkyl; C 4 -d 6 dialkyIaminoalkyl; or C 5 -C ⁇ 2 cycloalkyl; or, when bonding to the same nitrogen atom, together form a C 3 -C 9 alkylene or C -C 9 alkylene which is interrupted by -O-, - NR' 6 -, -S-, phenylene and/or substituted by oxo, OH, C 6 -C ⁇ 0 aryl;
  • R 9 is C ⁇ -C ⁇ 8 alkyl; C 2 -C 18 alkenyl; phenyl; C 7 -Cnphenylalkyl; C 5 -C ⁇ 2 cycloalkyl; C - C ⁇ phenylalkyl; C 6 -Ci 5 -bicycloalkyl, C 6 -C ⁇ 5 bicycloalkyl-alkyl, Ce-dsbicycloalkenyl, or C 7 - C ⁇ 5 tricycloalkyl
  • R 1 0 is C ⁇ -C 12 alkyl; phenyl; naphtyl or C 7 -C ⁇ alkylphenyl;
  • R 11 is H; C ⁇ -C 18 alkyl; C 3 -C 6 alkenyl; C 5 -C ⁇ 2 cycloalkyl; phenyl; naphthyl; biphenylyl; C 7 -Cn- phenylalkyl; C 7 -d alkylphenyl; halogen; C ⁇ -C ⁇ 8 alkoxy;
  • R 41 is H, d-C 18 alkyl; C 5 -d 2 cycIoalkyl; C 2 -C ⁇ 8 alkenyl; phenyl; C 7 -Cnphenylalkyl; C 7 - Cnalkylphenyl; OH; NH 2 ; NHR 7 ; NR 7 R8; SRS; halogen; COOH, COOR 4 ; -0-CO-R 5l -O-CO- OR 6j CONH 2 ; CONHR 7 ; CONR 7 R 8; COR 9 ; SO 2 -OR 4 ; SO 2 R 10 ; SOR,,; NO 2 ; CN;
  • Ru is H; C C 18 alkyl; C 5 -C ⁇ 2 cycloalkyl; C 2 -C 18 alkenyl; phenyl; C 7 -Cnphenylalkyl; C 7 - Cnalkylphenyl; OH; OR ⁇ ; NR 7 R 8 ; SR 1 ; halogen; COOH; COOR 4 ; CONH 2 ; CONHR 7 ; CONR 7 R 8 COR 9 ; SO 2 -OR 4; SO 2 R ⁇ 0 ; SO-Rn; NO 2 ; CN; R ⁇ , R 4 8 are independently from each other hydrogen; d-C ⁇ 8 alkyl; C 4 -C ⁇ 2 cycloalkyl; C 2 - C 18 alkenyl; phenyl; C 7 -d ⁇ phenylalkyl; C 7 -Cnalkylphenyl; -CH 2 CH(OR 5 o)R 5 i; -
  • R46, R47 are independently from each other hydrogen; C C ⁇ 8 -alkyl; C -d 2 cycloalkyl; C 2 - C ⁇ 8 alkenyl; phenyl; C 7 -d ⁇ phenylalkyl; C 7 -Cnalkylphenyl; CH 2 CH(OR 5 o)R 5 i; CH 2 CH(OR 5 2)CHOR 5 o; or R ⁇ , R 47 together form a C3-C 9 alkylene which may be interrupted by -O-, -NH-, -NR 7 -, -S- and or substituted by OH, C 6 -C 10 aryl;
  • R ⁇ is C r Ci 8 alkyl; C 5 -C ⁇ 2 cycloalkyl; C 2 -C ⁇ 8 alkenyl; phenyl; C 7 -d ⁇ phenylalkyl; C 7 - Cnalkylphenyl; -CH 2 CH(OR 5 o)R 5 ⁇ ; -CH 2 CH(OR 52 )CHOR 5 o; -COR 5 ,
  • R50, R52 are independently from each other H; C C ⁇ 8 alkyl; C 3 -d 8 alkenyl; C 5 -C ⁇ 2 cycloalkyl; d-C alkyl-cyclohexyl; C 6 -C 1 aryl; C- 7 -C-nphenyIalkyl; C 7 -d alkylphenyl;
  • R51 is d-C ⁇ 8 alkyl; C 2 -C 8 alkenyl; C 5 -C ⁇ 2 cycloalkyl; C ⁇ -C 4 alkyl-cyclohexyl; C 6 -C ⁇ 4 aryl; C -Cnphenylalkyl; C 7 -C ⁇ 4 alkylphenyl; C 6 -d 5 bicycloalkyl; C 6 -C ⁇ 5 bicycloalkenyl; C 6 - C ⁇ 5 tricycloalkyl;
  • R53 is H or OH; or is OR , where R'1 is as defined above;
  • R55 are independently from each other H; C 6 -C ⁇ 8 aryl; C 6 -d 8 aryl which is substituted by d-dsalkyl, Crd 8 alkoxy; or are C C 18 alkyl; C 3 -C ⁇ 8 alkyl which is interrupted by -O-; and
  • X is chloro or fluoro, preferably fluoro.
  • the reaction is preferably carried out in a polar solvent, especially a polar aprotic solvent, e.g. an ether, ester, amide, tertiary amine or suitable sulfoxide; preferred solvents are N,N'- dimethylformamide (DMF), N,N'-dimethylacetamide, N-methyl-2-pyrolidone, dimethylsulfoxide (DMSO), sulfolane, hexamethylphosphoramide, especially DMSO.
  • a polar aprotic solvents without an amino function are preferred.
  • the compound of the formula IX may be a primary or a secondary amine or NH 3 .
  • Amines like NH 2 NH 2) NH 2 OH are also suitable. Secondary amines may be advantageous in terms of higher reactivity, especially cyclic ones.
  • the amine of formula IX is often used in amounts from about one to 20 molar equivalents per equivalent X in the triazine educt of the formula I"; the amine is preferably used in excess (e.g. 2 to 20 molar equivalents on one equivalent X in the triazine educt); this is especially preferable in cases wherein formula IX comprises more than one (amino) reactive site.
  • the amine of formula IX may also be used in lower amounts (e.g. equimolar), preferably with addition of a base which may serve as a trap for the produced HX (HF or HCI).
  • the reaction temperature is, for example, between 50 °C and 200 °C. Most preferred is a reaction temperature between 80 and 160 °C.
  • reaction time is advantageously adjusted in relation to the reactivity of the amine.
  • R' ⁇ is H; CrC 20 alkyl; C 3 -C ⁇ 8 alkenyl; CrC 18 alkyl which is substituted by OH, C C 18 alkoxy, -
  • R' 2 , R' 3 are independently from each other, hydrogen; NH 2 ; C C 2 oalkyl; C C 18 alkyl substituted with OH, d-d 8 alkoxy; or R' 2 and R' 3 together form a C 3 -C 5 alkylene which may be interrupted by -O-, -NH-;
  • R_ t and R 5 independently are alkyl or hydroxyalkyl of 1 to 12 carbon atoms
  • R 1 is hydrogen
  • R ⁇ is hydrogen or OH
  • Hal stands for a halogen atom, preferably chloro
  • X is chloro or fluoro, preferably fluoro
  • R 44 is as defined for formula I'
  • a lewis acid preferably an aluminum halide
  • R' 2 , R' 3 are independently from each other, hydrogen, C C 2 oalkyl, C 2 -C 18 alkenyl; C 4 - C ⁇ 2 cycloalkyl; OH; NH 2 ; OR ⁇ 0 ; NHR 10 ; C C 18 alkyl substituted with phenyl, vinylphenyl, OH, C C ⁇ 8 alkoxy, C 5 -C ⁇ 2 cycIoalkoxy, C 3 -C 18 alkenyloxy, d-C ⁇ 8 alkylthio, phenylthio, phenylthio substituted by d-C 18 alkyl, phenyI-d-C 4 -alkylthio, -COOH, -CO-NH 2 , -CO-NHR 7 , -CO- N(R 7 )(R 8 ), NH 2 , NHR 7 , -N(R 7 )(R 8 ), -NH-CO-R 5 , phen
  • X is fluoro and Hal is chloro.
  • the intermediate formed after reaction step (a) may be isolated or, preferably, is further reacted in step (b) without isolation or purification.
  • Primary or secondary amino groups (R' 2 and/or R' 3 as hydrogen) may also be converted into secondary or tertiary amino groups within a subsequent reaction step, e.g. by alkylation or acylation according to methods known in the art.
  • p-standing phenolic OH groups may be etherified or esterified as described above.
  • An advantageous process for preparing the present compounds starts from cyanuric halide, preferably cyanuric chloride, reacting this educt with about one or about two equivalents of p- bromohalogenobenzene in a Grignard type reaction, where the halogen (in the below formulae denoted as X) is preferably chlorine or fluorine, and most preferably fluorine, to obtain an intermediate compound of the formula
  • This process may be carried out in analogy to methods known in the art, e.g. EP-A-577559.
  • cyanuric halide may be reacted with a non-phenolic benzene, e.g. a compound of the formula III'
  • those intermediate compounds still containing a reactive site on the triazine core may be reacted with a benzene, preferably a substituted one, in another reaction of Friedel-Crafts type (see e.g. US-4826978), or in analogy to coupling reactions described in J. Org. Chem. 66, 7125-8 (2001), to obtain the intermediate of formula l".
  • the target compound is one of formula I below
  • the benzene used for this reaction step comprises a resorcinol.
  • Substituents A other than aryl on the triazine core may conveniently be introduced in analogy to methods described by A. Furstner et al. (J. Am. Chem. Soc. 124, 13856 [2002]; Angew. Chem. Int. Ed. 41 , 609 [2002]; Angew. Chem. 115, 320 [2003]).
  • Phenolic OH groups, especially p-standing ones, in the intermediate thus obtained may be etherified or esterified according to methods known in the art (e.g. EP-A-434 608, H. Brunetti and C.E. L ⁇ thi, Helv. Chim. Acta 55, 1566 (1972); GB-A-975966); examples are reactions with suitable halogenides or epoxides such as of formulae
  • Hal is halogen, preferably Br or Cl, especially Br;
  • R'i is d-C 2 oalkyl; C 5 -d 2 cycloalkyl; C 3 -O 8 alkenyl; or has one of the meanings given for R-i of formula I, and R" ⁇ is a corresponding residue reduced by 2 carbon atoms, e.g.
  • C ⁇ -C ⁇ 8 alkyl C 5 -d 2 cycloalkyl; C -C ⁇ 6 alkenyl; d-C ⁇ 6 alkyl which is substituted by phenyl, vinylphenyl, C 5 -C ⁇ 2 cycloalkyl, OH, d-C ⁇ 8 alkoxy, C 5 -C ⁇ 2 cycloalkoxy, C 3 -C ⁇ 8 alkenyloxy, halogen, -COOH, -COOR 4 , -O-CO-R5, - O-CO-O-Ra, -CO-NH 2) -CO-NHR7, -CO-N(R 7 )(R 8 ), CN, NH 2 , NHR 7 , -N(R 7 )(R 8 ), -NH-CO-R 5 , phenoxy, d-d 8 alkyl-phenoxy, phenyl-C ⁇ -C -alkoxy, C 6 -C ⁇ 5 bicycloalk
  • this optional step of etherification or esterification may also be carried out after substitution of the para-halogeno group X by the aminic group as described above.
  • D is a group of of formula II', III or IV"
  • E is chloro or a group of the formula II'
  • R" ⁇ is as defined for R'-i, and all other symbols are as defined for formula I' above.
  • R 4 ⁇ and R 4 _v are hydrogen.
  • Preferred R'i or R" ⁇ independently are hydrogen or are as defined above for formula I'; R" ⁇ is especially preferred as hydrogen; other preferences are as described for formula I' above.
  • the compounds of formula I may also be prepared following one of the following synthetic routes.
  • R 4 has its previous significance and R'i is preferably H or is as defined for R ⁇ may be reacted with a chloride of formula CI-CO-A, e.g. a benzoyl chloride of one of the formulae:
  • an o-hydroxybenzamide of formula (4) may be reacted with a p- nitro-benzoyl chloride of formula:
  • an o- hydroxybenzamide of formula (4) may be reacted with a p-acylaminobenzoyl chloride having the formula:
  • R 33 is R 5 , OR 6 , COOR 6 , NHR 30 or NR 30 R 3 ⁇ where R 5 , R 6 , R 30 , R31 and Ru have their previous significance, to produce a compound having the formula:
  • R 60 is X or NR' 2 R' 3 as described above. Examples:
  • any radical as alkyl is branched or unbranched alkyl, for example embracing methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert- butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1- methylhexy], n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n- octyl, 2-ethyl hexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1, 3,3 ,5,
  • the radicals C 5 -C 12 cycloalkyl comprise cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl. Preference is given to cyclopentyl, cyclohexyl, cyclooctyl and cyclododecyl.
  • alkenyl embraces, inter alia, vinyl, allyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methylbut-2-enyl, n-oct-2- enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl or n-octadec-4-enyl.
  • Any hydrocarbon such as alkyl, alkenyl, alkylene, alkenylene interrupted by oxygen, sulfur and/or nitrogen atoms usually is interrupted by -O-, -NH-, -NR7-, -S-.
  • These moieties can be interrupted by one or more of these groups, one group in each case being inserted, in general into one bond, and hetero-hetero bonds, for example O-O, S-S, NH-NH, etc., not occurring; if the interrupted alkyl is additionally substituted, the substituents are generally not ⁇ to the heteroatom.
  • two or more interrupting groups of the type -O-, -NH-, -NR 7 -, -S- occur in one radical, they are usually identical.
  • R 2 and R 3 or R 7 and R 8 as alkylene which may be interrupted by -O-, -NH-, -NR 7 -, -S-, phenylene and/or substituted by oxo, OH, C 6 -C ⁇ 0 aryl, together with the nitrogen atom they are attached to, includes, for example, the residues of the formulae
  • Aryl is generally an aromatic hydrocarbon radical, for example phenyl, biphenylyl or naphthyl.
  • aryl may, for example, be selected from phenyl, naphthyl, biphenylyl, or a residue of the formulae preferred is phenyl, naphthyl, biphenylyl, especially phenyl.
  • Aralkyl is generally alkyl substituted by aryl, especially by phenyl; thus C 7 -C 2 oaralkyl comprises, for example, benzyl, ⁇ -methyl benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl and phenylhexyl; C 7 -Cnphenylalkyl preferably embraces benzyl, ⁇ - methylbenzyl and ⁇ , ⁇ -dimethyl benzyl.
  • Alkylphenyl and alkylphenoxy are alkyl-substituted phenyl and phenoxy, respectively.
  • a halogen substituent is -F, -Cl, -Br or -I; preference is given to -F or -Cl, especially -Cl, unless otherwise indicated.
  • C ⁇ -C 20 alkylene is, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, etc.
  • the alkyl chain here can also be branched, as in isopropylene, for example.
  • C 4 -C 12 cycloalkenyl is, for example 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2,4-cyclopentadien- 1-yl-, 2-cyclohexen-1-yl, 2-cyclohepten-1-yl or 2-cycloocten-1-yl.
  • C 6 -C ⁇ 5 bicycloalkyl is, for example, bornyl, norbornyl, [2.2.2]bicyclooctyl. Preference is given to bornyl and norbornyl, especially bornyl and norborn-2-yl.
  • C 6 -C 15 bicycloalkoxy is, for example, bornyloxy or norbom-2-yloxy.
  • C 6 -C ⁇ 5 bicycloalkyl-alkyI or -alkoxy is bicycloalkyl-substituted alkyl or alkoxy, the total number of carbon atoms being 6-15; examples are norbornane -2-methyl and norbornyl -2-methoxy.
  • C 6 -C ⁇ bicycloalkenyl is, for example, norbornenyl, norbornadienyl. Preference is given to norbornenyl, especially norbom-5-ene.
  • C 6 -C ⁇ 5 bicycloalkenylalkoxy is bicycloalkenyl-substituted alkoxy, the total number of carbon atoms being 6-15; one example is norborn-5-ene-2-methoxy.
  • C 6 -C 15 tricycloalkyl is, for example, 1-adamantyl, 2-adamantyl. Preference is given to 1- adamantyl.
  • C 6 -d 5 tricycloalkoxy is, for example, adamantyloxy.
  • C 3 -C ⁇ 2 heteroaryl is, preferably, pyridinyl, pyrimidinyl, triazinyl, pyrrolyl, furanyl, thiophenyl or quinolinyl.
  • A is H, d-Ci 8 alkyl; C 5 -C 12 cycloalkyl; C 2 -C 18 alkenyl; C 2 -C ⁇ 8 alkynyl; OR 45 , NR46R47, SR 8 ; or a residue of one of the formulae
  • each of Ri independently is phenyl; C ⁇ -C ⁇ 8 alkyl which is substituted by phenyl, vinylphenyl, C 5 -C ⁇ 2 cycIoalkyl, OH, C ⁇ -C ⁇ 8 alkoxy, C 5 -C ⁇ 2 cycloalkoxy, C 3 -d 8 alkenyloxy, halogen, -COOH, - COOR4, -O-CO-Rs, -O-CO-O-R 6 , -CO-NH 2 , -CO-NHR 7 , -CO-N(R 7 )(R 8 ), CN, NH 2 , NHR 7 , - N(R 7 )(R 8 ), -NH-CO-R5, phenoxy, Ci-Cisalkyl-phenoxy, phenyI-C C 4 -alkoxy, C 6 - C 15 bicycloalkoxy, C 7 -C 15 bicycloalkyl-alkoxy, C 7 -
  • R 2 , R 3 are independently from each other, hydrogen, d-C 20 alkyl, C 2 -d 8 alkenyl; C 6 -C 14 aryl; C 4 -C 12 cycloalkyl; C 7 -C 13 aralkyl; C 7 -C 13 alkylaryl; OH; NH 2 ; OR 10 ; NHR 10 ; C r C 18 alkyl substituted with phenyl, vinylphenyl, OH, C C 18 aIkoxy, C 5 -C 12 cycloalkoxy, C 3 -C 18 alkenyloxy, d-d 8 alkylthio, phenylthio, phenylthio substituted by d-C ⁇ 8 alkyl, phenyl-C C 4 -alkylthio, halogen, -COOH, -COOR4, -O-CO-R 5 , -O-CO-O-Re, -CO-NH 2 , -CO-
  • R 5 is d-C ⁇ 8 aIkyl; d-dsalkyl substituted by COOH, COOR*; C 2 -C 18 alkenyl; C 2 -C 18 alkenyl substituted by COOH or COORt; C 5 -C 12 cycloalkyl; phenyl; C 7 -d ⁇ phenylalkyl; C 7 - Cnalkylphenyl; C 6 -C ⁇ 5 bicycloalkyl; C 6 -C ⁇ 5 bicycloalkenyl; C 6 -C ⁇ 5 tricycloalkyl;
  • R 6 is C C 18 alkyl; C 3 -d 8 alkenyl; phenyl; C 7 -C 11 phenylalkyl; C 5 -d 2 cycloalkyl;
  • R'e is H; C C ⁇ 8 alkyl; C 3 -C ⁇ 8 alkenyl; phenyl; C 7 -Cnphenylalkyl; C 5 -C ⁇ 2 cycloalkyl;
  • R 7 and R 8 are independently phenyl; C ⁇ -C ⁇ 2 alkyl; C 7 -C ⁇ 3 aral yl; C7-C ⁇ 3 alkylaryl; C 3 - C ⁇ 2 alkoxyalkyl; C 4 -C ⁇ 6 dialkylaminoalkyl; or C 5 -C ⁇ 2 cycloalkyl; or, when bonding to the same nitrogen atom, together may form a C 3 -Cgalkylene or C 3 -C 9 alkylene which is interrupted by - O-, -NR' 6 -, -S-, phenylene and/or substituted by oxo, OH, C 6 -d 0 aryl;
  • R 9 is CrC ⁇ 8 alkyl; C 2 -C 18 alkenyl; phenyl; C 5 -C 12 cycloalkyl; C 7 -Cnphenylalkyl; C 6 -C 15 - bicycloalkyl, C 6 -C ⁇ 5 bicycloalkyl-alkyl, C 6 -C 15 bicycloaIkenyl, or C 7 -Ci 5 tricycloalkyl
  • R 10 is CrC ⁇ 2 alkyl; phenyl; naphtyl or C 7 -C ⁇ 4 alkylphenyl;
  • R 11 is H; d-C ⁇ 8 alkyl; C 3 -C 6 alkenyl; C 5 -C 12 cycloalkyl; phenyl; naphthyl; biphenylyl; C -dr phenylalkyl; C 7 -C 14 alkylphenyl; halogen; C C 18 alkoxy;
  • R3o, R31 are independently C ⁇ -C 12 alkyl; phenyl; or together, if attached to the same atom, are C 3 -C 9 alkylene or C 3 -C 8 alkylene which is interrupted by -O-, -NH-, -NR -, -S- and/or substituted by OH, C 6 -C ⁇ 0 aryl;
  • R 41 is H, C C 18 alkyl; C 5 -C ⁇ 2 cycloalkyl; C 2 -C 18 alkenyl; phenyl; d-d henylalkyl; C 7 - Cnalkylphenyl; OH; NH 2 ; NHR 7; NR 7 R 8 ; SR,; halogen; COOH, COOR ⁇ -O-CO-R 5 , -O-CO- OR 6 , CONH 2 ; CONHR 7 ; CONR 7 R 8; COR 9 ; SOr-OR* SO 2 R 10 ; SORn; NO 2 ; CN;
  • R M is H, C ⁇ -C ⁇ 8 alkyl; C 5 -d 2 cycloalkyl; C 2 -C ⁇ 8 alkenyl; phenyl; C 7 -Cnphenylalkyl; C 7 - Cnalkylphenyl; OH; OR*,, NR 7 R 8 , SR ⁇ , halogen; COOH, COOR 4 ; CONH 2 ; CONHR 7 ; CONR 7 R 8: COR 9 ; SO 2 -OR4 ; SO 2 R 10 ; SO-Rn; NO 2 ; CN;
  • R 45 , R ⁇ are independently from each other hydrogen; C ⁇ -d 8 alkyl; C -C ⁇ 2 cycloalkyl; C 2 - C ⁇ 8 alkenyl; phenyl; C 7 -Cnphenylalkyl; C 7 -Cnalkylphenyl; -CH 2 CH(OR5o)Rs ⁇ ; - CH 2 CH(OR 52 )CHOR 50 ;
  • R 46 , R 4 7 are independently from each other hydrogen; d-Ci8-alkyl; C 4 -C ⁇ 2 cycloalkyl; C 2 - C ⁇ 8 alkenyl; phenyl; C 7 -Cnphenylalkyl; C 7 -Cnalkylphenyl; CH 2 CH(OR 5 o)R 5 ⁇ ; CH 2 CH(OR 52 )CHOR5o; or R ⁇ , R 4 .7 together form a C 3 -C 9 alkylene which may be interrupted by -O-, -NH-, -NR 7 -, -S- and or substituted by OH, C 6 -C 10 aryl;
  • R 49 is C ⁇ -C ⁇ 8 alkyl; C 5 -d 2 cycloalkyl; C 2 -C ⁇ 8 alkenyl; phenyl; C 7 -Cnphenylalkyl; C 7 - Cnalkylphenyl; -CH 2 CH(OR5o)R5i; -CH 2 CH(OR 52 )CHOR5o; -COR 5 ,
  • R 50J R 52 are independently from each other H; CrC ⁇ 8 alkyl; C 3 -C 18 alkenyl; C 5 -C ⁇ 2 cycloalkyl; C ⁇ -C 4 alkyl-cyclohexyl; C 6 -C ⁇ 4 aryl; C 7 -Cnphenylalkyl; C 7 -d 4 alkylphenyl;
  • R 51 is C Ci 8 alkyl; C 2 -C ⁇ 8 alkenyl; C 5 -C ⁇ 2 cycloalkyl; CrC 4 aIkyl-cyclohexyl; C 6 -C ⁇ 4 aryl; C 7 -Cnphenylalkyl; C 7 -C ⁇ alkylphenyl; C 6 -d 5 bicycloalkyl; C 6 -C ⁇ 5 bicycIoalkenyl; C 6 - d 5 tricycloalkyl;
  • R ⁇ is H or OH; or is OR ⁇ where R ⁇ is as defined above;
  • R 54 , R 55 are independently from each other H; C 6 -C 18 aryl; C 6 -d 8 aryl which is substituted by d-C 18 alkyl, Crd 8 alkoxy; C ⁇ -C ⁇ 8 alkyl; C 3 -C ⁇ 8 alkyl which is interrupted by -0-; 5 6 .
  • R57 and R 58 independently are C 6 -d 8 aryl; C 6 -C ⁇ 8 aryl which is substituted by Crd 8 alkyl, d-C 8 alkoxy; C C ⁇ 8 alkyl; C 3 -C ⁇ 8 alkyl which is interrupted by -O-.
  • R- is preferably H, d-C ⁇ 8 alkyI; C 5 -C 12 cycloalkyl; C 3 -d 8 alkenyl; phenyl; C C ⁇ 8 alkyl, which is substituted with phenyl, vinylphenyl, OH, d-C ⁇ 8 alkoxy, C 5 -C ⁇ 2 cycloalkoxy, C 3 -C ⁇ 8 alkenyloxy, halogen, -COOH, -COORi, -O-CO-R 5 , -O-CO-O-R e , -CO-NH 2 , -CO-NHR 7 , -CO-N(R 7 )(R 8 ), CN, NH 2 , NHR 7 , -N(R 7 )(R 8 ), -NH-CO-R 5 , phenoxy, phenoxy substituted with C ⁇ -C ⁇ salkyl, phenyl-d-C 4 -
  • More preferred compounds of the formula I are those conforming to the formula
  • R 1 is H, d-C 20 alkyl; C 5 -C ⁇ 2 cycloalkyl; C 3 -d 8 alkenyl; C r C 18 alkyl which is substituted by C 5 -
  • Ri is d-C ⁇ 8 alkyl which is substituted by C 5 -d 2 cycloalkyl, OH, C C ⁇ 8 alkoxy, C 5 -
  • R 2 , R 3 are independently from each other, hydrogen, d ⁇ C 20 alkyl, C 2 -C 18 alkenyl; C 7 -
  • R 3 together form a C 3 -C 8 alkylene which may be interrupted by -O-, -NH-, -NR - and/or substituted by oxo, OH;
  • R 4 is CrC 18 alkyl; C 3 -C 8 alkenyl; phenyl; C 7 -C 11 phenylalkyl; cyclohexyl; C 3 -C 50 alkyl, which is interrupted by -O- and which can be substituted by OH; or is C 2 -C 12 hydroxyalkyl;
  • R 5 is C ⁇ -C ⁇ 8 alkyl; C C ⁇ 8 alkyl substituted by COOH, COOR ⁇ C 2 -d 8 alkenyl; C 2 -d 8 alkenyl substituted by COOH or COOR ⁇ - cyclohexyl; phenyl; C 7 -Cnphenylalkyl; C 7 -Cn alkyl phenyl;
  • R 6 is CrC ⁇ 8 alkyl; phenyl; d-Cnphenylalkyl;
  • R7 and R 8 are independently C ⁇ -C 12 alkyl; C7-Ci 3 phenylalkyl; C 3 -C ⁇ 2 alkoxyalkyl; C -
  • R 10 is C ⁇ -C ⁇ 2 alkyl; or C7-C ⁇ alkylphenyl;
  • R 44 is H, C r C 8 alkyI; OH; NR 7 R 8 .
  • A is of the formula II or IV;
  • R 1 is d-C ⁇ 8 alkyl which is substituted by OH, d-dsalkoxy, -COOR*, -O-CO-R 5 ;
  • R 2 , R 3 are independently from each other, hydrogen; NH 2 ; d-C 20 alkyl; O-C ⁇ 8 alkyl substituted with OH, d-C ⁇ 8 alkoxy; or R' 2 and R' 3 together form a C 3 -C 5 alkylene which may be interrupted by -O-, -NH-;
  • R 4 and R 5 independently are alkyl or hydroxyalkyl of 1 to 12 carbon atoms
  • R 41 is hydrogen
  • R ⁇ is hydrogen or OH; R 53 is OH.
  • Typical compounds of the formula I comprise those in which
  • A is H, d-C ⁇ 8 alkyl; C 5 -C ⁇ 2 cycloalkyl; C 2 -d 8 alkenyl; C 2 -C ⁇ 8 alkynyl; OR 45 , NR 46 R 47 , SR 48 ; or a residue with the formula:
  • R 1 phenyl; d-C ⁇ 8 alkyl, substituted with phenyl, vinylphenyl, OH, d-C ⁇ 8 alkoxy, C 5 - C ⁇ cycloalkoxy, C 3 -C ⁇ 8 alkenyIoxy, halogen, -COOH, -COOR 4 , -O-CO-R5, -O-CO-O-R 6 , -CO- NH 2 , -CO-NHR 7 , -CO-N(R 7 )(R 8 ), CN, NH 2 , NHR 7 , -N(R 7 )(R 8 ), -NH-CO-R 5 , phenoxy, phenoxy substituted by C ⁇ -d 8 alkyl, phenyl-C ⁇ -C 4 -alkoxy, C 6 -C 15 bicycloalkoxy, C 6 -C ⁇ 5 bicycloalkyl- alkoxy, C 6 -C ⁇ 5 bicycloalkenyl-
  • R 2 , R 3 are independently from each other, hydrogen, C C 20 alkyl, C 2 -C 18 alkenyl; C 8 -C ⁇ 4 aryl; C 4 -C ⁇ 2 cycloalkyl, C 7 -C ⁇ 3 aralkyl, C 7 -C 13 alkylaryl; C ⁇ -C 18 alkyl substituted with phenyl, vinylphenyl, OH, C ⁇ -C 18 alkoxy, C 5 -d 2 cycloalkoxy, C 3 -d 8 alkenyloxy, halogen, -COOH, - COOR 4 , -O-CO-R 5 , -O-CO-O-Re, -CO-NH 2 , -CO-NHR 7 , -CO-N(R 7 )(R 8 ), CN, NH 2 , NHR 7 , - N(R 7 )(R 8 ), -NH-CO-R 5 , phenoxy, phenoxy substituted by C
  • R 4 is C ⁇ -C 18 alkyl; C 3 -d 8 alkenyl; phenyl; d-Cn-phenylalkyl; C 5 -C ⁇ 2 cycloalkyl; or C 3 -C 5 oalkyl, which is interrupted by one to several -O-, -NH-, -NR -, -S- groups, and which can be substituted by OH, phenoxy or C 7 -C 18 alkylphenoxy; or C 2 -C 12 -Hydroxyalkyl
  • R 5 is C C 18 alkyl; C C ⁇ 8 alkyl substituted with COOH or COOR ⁇ C 2 -C ⁇ 8 alkenyl; C 2 -d 8 alkenyl substituted with COOH or COOR 4 ; C 5 -C ⁇ 2 cycloalkyl; phenyl; C 7 -C 1 phenylalkyl; C7-C 1 1- alkylphenyl; C 6 -C 15 bi
  • R 6 is C ⁇ -C ⁇ 8 alkyl; C 3 -C ⁇ 8 alkenyl; phenyl; d-Cn-phenylalkyl; C 5 -C ⁇ 2 cycloalkyl;
  • R 7 and R 8 are independently phenyl; C ⁇ -C 12 alkyl; C 7 -C 13 alkylaryl; C 7 -C 13 aralkyl; C 3 - C ⁇ 2 alkoxyalkyl; C -d 6 -dialkylaminoalkyl; or C 5 -C 12 cycloalkyl; or together form a C 3 -C 9 alkylene which may be interrupted by oxygen, sulfur and nitrogen atoms, and or substituted by OH, C 6 -do aryl;
  • Rg is d-C ⁇ 8 alkyl; C 2 -C ⁇ 8 alkenyl; phenyl; C 5 -d 2 cycloalkyl; C 7 -drphenylalkyl; C 6 - Ci 5 bicycloalkyl, C 6 -Ci 5 bicycIoalkyl-alkyl, Ce-Cisbicycloalkenyl, or C 6 -C ⁇ 5 tricycloalkyl;
  • R 10 is C ⁇ -C ⁇ 2 alkyl; phenyl; Naphtyl or C 7 -C 14 alkylphenyl;
  • R 11 is C C 18 alkyl; C 3 -C 6 alkenyl; C 5 -C ⁇ 2 cycloalkyl; phenyl; naphthyl; biphenylyl; C 7 -C 11 - phenylalkyl; C 7 -C ⁇ 4 alkylphenyl; halogen; C Ci 8 alkoxy;
  • R 30 , R 31 are independently C C ⁇ 2 alkyl; phenyl; or together form a C 3 -Cg alkylene which may be interrupted by oxygen, sulfur and nitrogen atoms, and or substituted by OH, C 6 -C 10 aryl;
  • R 41 is H, d-C ⁇ 8 alkyl; C 5 -C ⁇ 2 cycloalkyl; C 2 -C ⁇ 8 alkenyl; phenyl; C 7 -Cn-phenylaIkyl; C 7 - Cnalkylphenyl; OH; NH 2 ; NHR 7 ; NR 7 R 8 , SR ⁇ halogen; COOH, COOR 4 ; -O-CO-R 5 , -O-CO- OR 6 , CONH 2 ; CONHR 7 ; CONR 7 R 8; COR 9 ; SO 2 -OR4 ; SO 2 R ⁇ 0 ; SORn; NO 2 ;
  • ra is C ⁇ -C ⁇ 8 alkyl; C 5 -C ⁇ 2 cycloalkyl; C 2 -d 8 alkenyl; phenyl; C 7 -d ⁇ -phenylalkyl; C - Cnalkylphenyl; -CH 2 CH(OR 5 o)R 5 ⁇ J -CH 2 CH(OR52)CHOR5o.-COR 5 ,
  • R 50 , R 52 are independently from each other H; d-C ⁇ 8 alkyl; C 3 -C 18 alkenyl; C 5 -C ⁇ 2 cycloalkyl; d-C 4 alkyl-cyclohexyl (not C 5 -d 2 alkyl-cyclohexyl); C 6 -C ⁇ 4 -aryl; C -Cn-phenylalkyl; C 7 - C ⁇ 4 alkylphenyl.
  • R 5 ⁇ is CrC ⁇ 8 alkyl; C 2 -C ⁇ 8 alkenyl; C 5 -C 12 cycloalkyl; d-C 4 alkyl-cyclohexyl; C 6 -C ⁇ 4 -aryl; C 7 -Cn- phenylalkyl; C 7 -d 4 alkyl phenyl; C 6 -C-
  • R 54 , R 55 are independently from each other H; C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C1-C18 alkyl, C 1 -C 1 8 alkoxy; C C ⁇ 8 alkyl; C 3 -d 8 alkyl which is interrupted by -O-; and
  • R56, R57 and R 58 independently are phenyl; C 7 -d 8 alkylphenyl or-alkoxyphenyl; C ⁇ -C ⁇ 8 alkyl; C 3 -d 8 alkyl interrupted by -O-.
  • R 2 , R 3 are independently from each other C 2 -C ⁇ 8 alkenyl; C 6 -C ⁇ 4 aryl; C 7 -d 3 alkylaryl; C1-C1 8 alkyl substituted with phenyl, vinylphenyl, OH, C C ⁇ 8 alkoxy, C 5 -C 12 cycloalkoxy, C 3 - C ⁇ 8 alkenyloxy, halogen, -COOH, -COOR t , -O-CO-R 5 , -O-CO-O-R 6 , -CO-NH 2 , -CO-NHR7, - CO-N(R 7 )(R 8 ), CN, NH 2 , NHR 7 , -N(R 7 )(R 8 ), -NH-CO-R 5 , phenoxy, phenoxy substituted by C C ⁇ 8 alkyl, phenyl-d-d-alkoxy, C 6 -C ⁇ 5 bicycloalkoxy
  • R 100 is as previously defined for R-i or is H, CrCi 8 alkyl; C 5 -d 2 cycloalkyl; C 3 -C ⁇ 8 alkenyl; phenyl. Examples are compounds of the formula Id
  • R 2] R 3 are independently from each other, hydrogen, d-doalkyl, C 2 -d 8 alkeny!; C 6 -d 4 aryl; C 4 -C ⁇ 2 cycloaIkyl, C7-C ⁇ 3 aralkyl, C 7 -C ⁇ 3 alkylaryl; C ⁇ -C ⁇ 8 alkyl substituted with phenyl, vinylphenyl, OH, d-C 18 alkoxy, C 5 -C 12 cycloalkoxy, C 3 -C ⁇ 8 alkenyloxy, halogen, -COOH, - COOR4, -O-CO-R 5j -O-CO-O-R 6 , -CO-NH 2 , -CO-NHR7, -CO-N(R 7 )(R 8 ), CN, NH 2 , NHR 7 , - N(R 7 )(R 8 ), -NH-CO-R 5 , phenoxy, phenoxy substituted by
  • R t is C C 18 alkyl; C 3 -C ⁇ 8 alkenyl; phenyl; C 7 -Cn-phenylalkyl; C 5 -d 2 cycloalkyl; or C 3 -C 50 alkyl, which is interrupted by one to several -O-, -NH-, -NR 7 -, -S- groups, and which can be substituted by OH, phenoxy or C 7 -d 8 alkylphenoxy; or C 2 -C 12 -Hydroxyalkyl Rs is H; C C ⁇ 8 alkyl; C ⁇ -C ⁇ 8 alkyl substituted with COOH or COOR 4 ; C 2 -C ⁇ 8 alkenyl; C 2 - C 18 alkenyl substituted with COOH or COOR 4 ; C 5 -C ⁇ 2 cycloalkyl; phenyl; C 7 -Cn-phenylalkyl; C 7 -Cn-alkylphenyl; C 6
  • R 6 is H; CrC 18 alkyl; C 3 -C ⁇ 8 alkenyl; phenyl; C 7 -Cn-phenylalkyl; C 5 -C ⁇ 2 cycloalkyl;
  • R 7 and R 8 are independently phenyl; d-C ⁇ alkyl; C 7 -C 13 alkylaryl; C 7 -C 13 aralkyl; C 3 - C ⁇ 2 aIkoxyalkyl; C 4 -C ⁇ e-dialkylaminoalkyl; or C 5 -C ⁇ 2 cycloalkyl; or together form a C 3 -C 9 alkylene which may be interrupted by oxygen, sulfur and nitrogen atoms, and or substituted by OH, C 6 -C 10 aryl.
  • R 9 is C C ⁇ 8 alkyl; C 2 -C ⁇ 8 alkenyl; phenyl; C 5 -d 2 cycloalkyl; C 7 -C ⁇ phenylalkyl; C 6 - C 15 bicycloalkyl, C 6 -C ⁇ 5 bicycloalkyl-alkyl, C 6 -C 15 bicycloalkenyl, or C 6 -C ⁇ 5 tricycloalkyl;
  • R 10 is C ⁇ -C 12 alkyl; phenyl; Naphtyl or C 7 -C ⁇ 4 alkylphenyl;
  • Rn is d-C ⁇ 8 alkyl; C 3 -C 6 alkenyl; C 5 -d 2 cycloalkyl; phenyl; naphthyl; biphenylyl; C 7 -d phenylalkyl; C7-C ⁇ alkylphenyl; halogen; Crd 8 alkoxy;
  • R 3 o, R 3 1 are independently d-C ⁇ 2 alkyl; phenyl; or together form a C 3 -Cg alkylene which may be interrupted by oxygen, sulfur and nitrogen atoms, and or substituted by OH, C 6 -do aryl;
  • R 41 is H, C ⁇ -C ⁇ 8 alkyl; C 5 -C 12 cycloalkyl; C 2 -C 18 alkenyl; phenyl; C 7 -Cn-phenylaIkyl; C 7 - Cnalkylphenyl; OH; OR.,; NH 2 ; NHR 7 ; NR 7 R 8 , SR,, halogen; COOH, COOR,; -O-CO-R 5 , -O- CO-OR 6 , CONH 2 ; CONHR 7 ; CONR 7 R 8 ; COR 9 ; SO 2 -OR 4; SO 2 R ⁇ 0 ; SORn; N0 2 ;
  • R ⁇ is d-C 18 alkyl; C 5 -C 12 cycloalkyl; C 2 -C 18 alkenyl; phenyl; C 7 -d phenylalkyl; C 7 - Cnalkylphenyl; -CH 2 CH(OR 5 o)Rs ⁇ J -CH 2 CH(OR 52 )CHOR5o, -COR 5 , R 50 , R52 are independently from each other H; C C 18 alkyl; C 3 -C ⁇ 8 alkenyl; C 5 -d 2 cycloalkyl; d-dalkyl-cyclohexyl (not Cs-C ⁇ alkyl-cyclohexyl); C 6 -C ⁇ 4 -aryl; C 7 -Cn-phenylalkyl; C 7 -
  • R 51 is C C ⁇ 8 alkyl; C 2 -C 18 alkenyl; C 6 -d 2 cycloalkyl; d-C 4 alkyl-cyclohexyl; C 6 -C ⁇ 4 -aryl; C 7 -Cn- phenylalkyl; C 7 -C 4 alkyl phenyl; C 6 -C ⁇ 5 bicycloalkyl; C 6 -C ⁇ 5 bicycloalkenyl; C 6 -C ⁇ 5 tricycloalkyl;
  • Rs 4 , R 5 5 are independently from each other H; C 6 -d 8 aryl; C 6 -C 18 aryl which is substituted by d-C ⁇ 8 alkyl, d-C ⁇ 8 alkoxy; C ⁇ -C 18 alkyl; C ⁇ -C ⁇ 8 alkyl which is interrupted by -0-.
  • R 2l R 3 are independently from each other, hydrogen, CrC 20 alkyl, C 2 -C 18 alkenyl; C 6 -C 14 aryl; C 4 -C 12 cycloalkyl, C 7 -C 13 aralkyl, C 7 -C 13 alkylaryl; C C 18 alkyl substituted with phenyl, vinylphenyl, OH, d-C ⁇ 8 alkoxy, C 5 -d 2 cycloalkoxy, C 3 -C ⁇ 8 alkenyloxy, halogen, -COOH, - COOR 4 , -O-CO-R 5 , -O-CO-O-Re, -CO-NH 2 , -CO-NHR 7 , -CO-N(R 7 )(R 8 ), CN, NH 2 , NHR 7 , - N(R 7 )(R 8 ), -NH-CO-R 5) phenoxy, phenoxy substituted by C C 1s alky
  • R 4 is C ⁇ -C ⁇ 8 alkyl; C 3 -C 18 alkenyl; phenyl; C 7 -Cn-phenylalkyl; C 5 -C ⁇ cycloalkyl; or C 3 -C 50 alkyl, which is interrupted by one to several -O-, -NH-, -NR 7 -, -S- groups, and which can be substituted by OH, phenoxy or C 7 -C ⁇ 8 alkylphenoxy; or C 2 -C ⁇ 2 -Hydroxyalkyl
  • R 5 is H; d-C ⁇ 8 alkyl; C ⁇ -C 18 alkyl substituted with COOH or COOR 4 ; C 2 -C 18 alkenyl; C 2 - C ⁇ 8 alkenyl substituted with COOH or COOR 4 ; C 5 -C ⁇ 2 cycloaIkyI; phenyl; C 7 -Cn-phenylalkyl; C 7 -Cn-alkylphenyl; C 6 -d 5 bicycloalkyl; C 6 -C 15 bicycloalkenyl; C 6 -C ⁇ 5 tricycloalkyl;
  • R 6 is H; C ⁇ -C ⁇ 8 alkyl; C 3 -C ⁇ 8 alkenyl; phenyl; d-Cn-phenylalkyl; C 5 -C ⁇ 2 cycloalkyl;
  • R 7 and R 8 are independently phenyl; d-C 12 alkyl; C 7 -C 13 alkylaryl; C 7 -C ⁇ 3 aralkyl; C 3 - C ⁇ 2 alkoxyalkyl; C 4 -Ci 6 -dialkylaminoalkyl; or C 5 -C ⁇ 2 cycloalkyl; or together form a C 3 -C 9 alkylene which may be interrupted by oxygen, sulfur and nitrogen atoms, and or substituted by OH, C 6 -do aryl.
  • Rg is C C ⁇ 8 alkyl; C 2 -C 18 alkenyl; phenyl; C 5 -d 2 cycloalkyl; C 7 -Cn-phenylalkyl; C 6 - C 15 bicycIoalkyl, C 6 -C 15 bicycloalkyl-alkyl, C 6 -C 15 bicycloalkenyl, or C 6 -C 16 tricycloalkyl;
  • R10 is d-C ⁇ 2 alkyl; phenyl; Naphtyl or C 7 -C ⁇ 4 alkylphenyl;
  • R 11 is C C ⁇ 8 alkyl; C 3 -C 6 alkenyl; C 5 -C 12 cycloalkyl; phenyl; naphthyl; biphenylyl; C 7 -Cn- phenylalkyl; C -d 4 alkylphenyl; halogen; d-C ⁇ 8 alkoxy;
  • R3o, R31 are independently C C 12 alkyl; phenyl; or together form a C 3 -C 9 alkylene which may be interrupted by oxygen, sulfur and nitrogen atoms, and or substituted by OH, C 6 -d 0 aryl.
  • Ro is C ⁇ -C ⁇ 8 alkyl; C 5 -d 2 cycloalkyl; C 2 -C ⁇ 8 alkenyl; phenyl; C 7 -d ⁇ -phenylalkyl; C 7 - Cnalkylphenyl; -CH 2 CH(OR 5 o)R 5 ⁇ J -CH 2 CH(OR 52 )CHOR5o. -COR 5 ,
  • R50, R 52 are independently from each other H; C C ⁇ 8 alkyl; C 3 -C ⁇ 8 alkenyl; C 5 -C 12 cycloalkyl; d-dalkyl-cyclohexyl (not C 5 -C 12 alkyl-cyclohexyl); C 6 -C ⁇ 4 -aryl; C 7 -Cn-phenylalkyl; C 7 -
  • R5 1 is C ⁇ -C ⁇ 8 alkyl; C 2 -d 8 alkenyl; C 5 -d 2 cycloalkyl; d-C 4 alkyl-cyclohexyl; C 6 -C ⁇ 4 -aryl; C 7 -Cn- phenylalkyl; C 7 -C 4 alkylphenyl; C 6 -C ⁇ 5 bicycloalkyl; C 6 -C ⁇ 5 bicycloalkenyl; C 6 -Ci 5 tricycloalkyl;
  • R 54 are independently from each other H; C 6 -C ⁇ 8 aryl; C 6 -C 18 aryl which is substituted by C ⁇ -C ⁇ 8 alkyl, C ⁇ -C 18 alkoxy; d-C 18 alkyl; C ⁇ -C 18 alkyl which is interrupted by -O-;
  • Ri is C 3 -C 50 alkyl, which is interrupted by one to several oxygen atoms, or/and which is substituted by OH, phenoxy or C 7 -d 8 alkyl phenoxy;
  • R 2 , R 3 are independently from each other, hydrogen, C ⁇ -C 20 alkyl, C 2 -C ⁇ 8 alkenyl; C 8 -Ci 4 aryl; C 4 -C ⁇ 2 cycloalkyl, C 7 -C ⁇ 3 aralkyl.
  • C 7 -C ⁇ 3 alkylaryl C C ⁇ 8 alkyl substituted with phenyl, vinylphenyl, OH, d-C ⁇ 8 alkoxy, C 5 -C 12 cycloalkoxy, C 3 -C 18 alkenyloxy, halogen, -COOH, - COOR ⁇ -O-CO-R5, -O-CO-O-R 6j -CO-NH 2 , -CO-NHR 7 , -CO-N(R 7 )(R 8 ), CN, NH 2 , NHR 7 , - N(R 7 )(R 8 ), -NH-CO-R 5 , phenoxy, phenoxy substituted by C C ⁇ 8 alkyl, phenyl-CrC -alkoxy, C 6 -C ⁇ 5 bicycloalkoxy, C 6 -d 5 bicyc]oalkyl-alkoxy, C 6 -C ⁇ 5 bicycloalkenyl-alkoxy
  • R 4 is C C 18 alkyl; C 3 -C ⁇ 8 alkenyl; phenyl; C 7 -Cn-phenylalkyl; C 5 -C 12 cycloalkyl; or C 3 -C 5 oalkyl, which is interrupted by one to several -O-, -NH-, -NR 7 -, -S- groups, and which can be substituted by OH, phenoxy or C 7 -d 8 alkyl phenoxy; or C 2 -C 12 -Hydroxyalkyl
  • R 5 is H; d-d.alkyl; C ⁇ -C 18 alkyl substituted with COOH or COOR 4 ; C 2 -C 18 alkenyl; C 2 - C ⁇ 8 alkenyl substituted with COOH or COORi; C 5 -d 2 cycloalkyl; phenyl; C 7 -Cn-phenylalkyl; C 7 -Cn-alkylphenyl; C 6 -C 15 bicycloalkyl; C 6 -C ⁇ 5 bicycloalkenyl; C 6 -C 15 tricycloalkyl;
  • R 6 is H; C 1 -C 18 alkyl; C 3 -C 18 alkenyl; phenyl; C 7 -Cn-phenylalkyl; C 5 -C 12 cycloalkyl;
  • R 7 and R 8 are independently phenyl; CrC 12 alkyl; C 7 -C 13 alkylaryl; C 7 -C 13 aralkyl; C 3 - C 12 alkoxyalkyl; C -C ⁇ e-dialkylaminoalkyl; or C 5 -C ⁇ 2 cycloalkyl; or together form a C 3 -C 9 alkylene which may be interrupted by oxygen, sulfur and nitrogen atoms, and or substituted by OH, C 6 -C 10 aryl.
  • R 9 is d-Cisalkyl; C 2 -C ⁇ 8 alkenyl; phenyl; C 5 -d 2 cycloalkyl; C 7 -C ⁇ phenylalkyl; C 6 - C 15 bicycloalkyl, C 6 -C ⁇ 5 bicycloalkyl-alkyl, C 6 -Ci5bicycloaIkenyl, or C6-d 5 tricycloalkyl;
  • R 1 0 is C r C ⁇ 2 alkyl; phenyl; Naphtyl or C 7 -d 4 alkylphenyl; Rn is C ⁇ -C ⁇ 8 alkyl; C 3 -C 6 alkenyl; C 5 -C ⁇ 2 cycloalkyl; phenyl; naphthyl; biphenylyl; C 7 -Cn- phenylalkyl; C -C ⁇ 4 alkylphenyl; halogen; C ⁇ -C 18 alkoxy;
  • R 3 1 are independently C 1 -C 12 alkyl; phenyl; or together form a C 3 -C 9 alkylene which may be interrupted by oxygen, sulfur and nitrogen atoms, and or substituted by OH, C 6 -C ⁇ 0 aryl.
  • R 41 is H, C ⁇ -C ⁇ 8 alkyl; C 3 -C ⁇ 2 cycloalkyl; C 2 -C 18 alkenyl; phenyl; C 7 -C ⁇ phenylalkyl; C 7 - Cualkylph ⁇ nyl; OH; OR.,; NH 2 ; NHR 7 ; NR 7 R ⁇ , SR-,, halogen; COOH, COOR,; -O-CO-R5, -O- CO-ORe, CONH 2 ; CONHR 7 ; CONR 7 R 8; COR 9 ; SOa-OR* SO 2 R ⁇ 0 ; SORn; NO 2 ;
  • R42, 43 are independently from each other substituted phenyl, by one or more from the following substituents vinylphenyl, OH, NR 2 R 3 , OR ⁇ , SO 2 OR4, SO2R10, SORn, NO 2 ; C7-C 1 1- phenylalkyl; C 7 -Cnalkylphenyl; SRi, halogen; COOH, COOR 4 ; -O-CO-R 5 , -0-CO-OR 6 , CONH 2 ; CONHR 7 ; CONR 7 R 8; COR 9 ; SOrOR* SO 2 R ⁇ 0 ; SO-Rn; NO 2 ; or R ⁇ , R ⁇ are connected together by a C 3 -C 5 alkenyl chain, containing one or two double bonds, and which can be substituted by Ci-Cs-alkoxy, d-C ⁇ 8 alkyl, NR 7 R 8
  • ra is C r C ⁇ 8 alkyl; C 5 -d 2 cycloalkyl; C 2 -C ⁇ 8 alkenyl; phenyl; C 7 -Cn-phenylalkyl; C 7 - Cnalkylphenyl; -CH 2 CH(OR 5 o)R 5 ⁇ J -CH 2 CH(OR 5 2)CHOR5o, -COR 5 ,
  • R 50 , R 52 are independently from each other H; C C ⁇ 8 alkyl; C 3 -d 8 alkenyl; C 5 -C ⁇ 2 cycloalkyl;
  • R 51 is C r C ⁇ 8 alkyl; C 2 -C ⁇ 8 alkenyl; C 5 -C ⁇ 2 cycloalkyl; C C 4 alkyl-cyclohexyl; C 6 -C 14 -aryl; C 7 -C ⁇ phenylalkyl; C 7 -d 4 alkyIphenyl; C 6 -C 15 bicycloalkyl; C 6 -C ⁇ 5 bicycloalkenyl; C 6 -C ⁇ 5 tricycloalkyl;
  • R54, R55 are independently from each other H; C 6 -C ⁇ 8 aryl; C 6 -d 8 aryl which is substituted by C 1 -C 18 alkyl, C C ⁇ 8 alkoxy; C C ⁇ 8 alkyl; d-C 18 alkyl which is interrupted by -O-.
  • Ci-d 8 alkyl C 5 -C ⁇ 2 cycloalkyl; C 3 -d 8 alkenyl; phenyl; d-C ⁇ 8 alkyl, which is substituted with phenyl, vinylphenyl, OH, d-d ⁇ alkoxy, C 5 -C 12 cycloalkoxy, C 3 -d 8 alkenyloxy, halogen, - COOH, -COOR 4 , -O-CO-R 5j -O-CO-O-R 6 , -CO-NH 2 , -CO-NHR 7 , -CO-N(R 7 )(R 8 ), CN, NH 2 , NHR 7 , -N(R 7 )(R 8 ), -NH-CO-R 5 , phenoxy, phenoxy substituted with C ⁇ -C ⁇ 8 alkyl, phenyl-d-d- alkoxy, Ce-d 5 bicycloalkoxy, C 6
  • R 2 , R 3 are independently from each other, hydrogen, d-doalkyl, C 2 -C ⁇ 8 alkenyl; C 6 -Ci 4 aryl; C 4 -C ⁇ 2 cycloalkyl, C 7 -C ⁇ 3 aralkyl, C 7 -d 3 alkylary[; C1-C1 8 alkyl substituted with phenyl, vinylphenyl, OH, C C 18 alkoxy, C 5 -C 12 cycloalkoxy, C 3 -C ⁇ 8 alkenyloxy, halogen, -COOH, - COOR 4 , -O-CO-R 5 , -O-CO-O-R 6 , -CO-NH 2 , -CO-NHR 7l -CO-N(R 7 )(R 8 ), CN, NH 2 , NHR 7 , - N(R 7 )(R 8 ), -NH-CO-R 5 , phenoxy, phen
  • R 4 is d-Cisalkyl; C 3 -C 18 alkenyl; phenyl; C 7 -Cn-phenylalkyl; C 5 -d 2 cycloalkyl; or C 3 -C 50 alkyl, which is interrupted by one to several -O-, -NH-, -NR 7 -, -S- groups, and which can be substituted by OH, phenoxy or C 7 -C ⁇ 8 alkylphenoxy; or C 2 -C ⁇ 2 -Hydroxyalkyl
  • R 5 is H; d-C 18 alkyl; C ⁇ -C ⁇ 8 alkyl substituted with COOH or COOR*; C 2 -C ⁇ 8 alkenyl; C 2 - C ⁇ 8 alkenyl substituted with COOH or COOR*; C 5 -d 2 cycloalkyl; phenyl; C 7 -Cn-phenylalkyl; C 7 -C ⁇ alkylphenyl
  • R 6 is H; d-C ⁇ alkyl; C 3 -C ⁇ 8 alkenyl; phenyl; C 7 -Cn-phenylalkyl; C 5 -C ⁇ 2 cycloalkyl;
  • R 7 and R 8 are independently phenyl; d-d 2 alkyl; C 7 -C 1 3 alkylaryl; C 7 -C 13 aralkyl; C 3 - C ⁇ 2 alkoxyalkyl; C 4 -d 6 -dialkylaminoalkyl; or C -C 12 cycloalkyl; or together form a C 3 -C 9 alkylene which may be interrupted by oxygen, sulfur and nitrogen atoms, and or substituted by OH, C 6 -C ⁇ 0 aryl.
  • R 9 is d-C ⁇ 8 alkyl; C 2 -O 8 alkenyl; phenyl; C 5 -d 2 cycloalkyl; C 7 -Cn-phenylalkyl; C 6 - C ⁇ 5 bicycloalkyl, C 6 -C ⁇ 5 bicycloalkyl-alkyl, C 6 -C ⁇ 5 bicycloalkenyl, or Ce-C ⁇ 5 tricycloalkyl;
  • R 10 is C C ⁇ 2 alkyl; phenyl; Naphtyl or C 7 -C ⁇ 4 alkylphenyl;
  • Rn is C ⁇ -C ⁇ 8 alkyl; C 3 -C 6 alkenyl; Cs-C ⁇ cycloalkyl; phenyl; naphthyl; biphenylyl; C 7 -Cn- phenylalkyl; C -C ⁇ 4 alkylphenyl; halogen; d-C ⁇ 8 alkoxy;
  • R 12 is phenyl, vinylphenyl, OH, NR 2 R 3 , ORa, SO 2 OR 4 , SO 2 R ⁇ 0 , SORn, NO 2 ; C 7 -Cn- phenylalkyl; C 7 -Cn alkyl phenyl; SR ⁇ , halogen;
  • R 3 o > R31 are independently C C 2 alkyl; phenyl; or together form a C 3 -C 9 alkylene which may be interrupted by oxygen, sulfur and nitrogen atoms, and or substituted by OH, C 6 -C ⁇ 0 aryl.
  • Ra is d-C 18 alkyl; C 5 -d 2 cycloalkyl; C 2 -O 8 alkenyl; phenyl; C 7 -Cn-phenylalkyl; C 7 - Cnalkylphenyl; -CH 2 CH(OR5o)R 5 ⁇ , -CH 2 CH(OR 52 )CHOR5o, -COR 5 ,
  • R 50 , R 52 are independently from each other H; C ⁇ -C ⁇ 8 alkyl; C 3 -C ⁇ 8 alkenyl; C 5 -C 2 cycloalkyl; d-C 4 alkyl-cyclohexyl (not C 5 -d 2 alkyl-cyclohexyl); C 6 -C ⁇ 4 -aryl; C 7 -Cn-phenylalkyl; C 7 - C ⁇ alkyl phenyl.
  • R 51 is C C ⁇ 8 alkyl; C 2 -C ⁇ 8 alkenyl; C 5 -C ⁇ 2 cycloalkyl; C C 4 alkyl-cyclohexyl; C 6 -C ⁇ 4 -aryl; C 7 -Cn- phenylalkyl; C 7 -d 4 alkyl phenyl; C 6 -d 5 bicycloalkyl; C 6 -C ⁇ 5 bicycloalkenyl; C -C ⁇ 5 tricycloalkyl; R54, R55 are independently from each other H; C 6 -C ⁇ 8 aryl; C 6 -d 8 aryl which is substituted by C ⁇ -C ⁇ 8 alkyl, d-C ⁇ 8 alkoxy; C C ⁇ 8 alkyl; C C ⁇ 8 alkyl which is interrupted by -O-.
  • R-i H C ⁇ -C ⁇ 8 alkyl; C 5 -C ⁇ 2 cycloalkyl; C 3 -C ⁇ 8 alkenyl; phenyl; C ⁇ -C ⁇ 8 alkyl, which is substituted with phenyl, vinylphenyl, OH, C C ⁇ 8 alkoxy, C 5 -C ⁇ 2 cycloalkoxy, C 3 -C 18 alkenyloxy, halogen, - COOH, -COOR,, -O-CO-R 5 , -O-CO-O-R 6 , -CO-NH 2 , -CO-NHR 7 , -CO-N(R 7 )(R 8 ), CN, NH 2 , NHR 7 , -N(R 7 )(R 8 ), -NH-CO-R 5) phenoxy, phenoxy substituted with C ⁇ -C ⁇ 8 alkyl, phenyl-d-d- alkoxy, C 6 -C 15 bicyc
  • R 2 , R 3 are independently from each other, hydrogen, d-C 2 oalkyl, C -C ⁇ 8 alkenyl; C 6 -C ⁇ aryl; C 4 -C ⁇ 2 cycloalkyl, C 7 -C ⁇ 3 aralkyl, C 7 -C 3 alkylaryl; C ⁇ -C ⁇ 8 alkyl substituted with phenyl, vinylphenyl, OH, C ⁇ -C ⁇ 8 alkoxy, C 5 -d 2 cycloalkoxy, C 3 -C 8 alkenyloxy, halogen, -COOH, - COOR 4 , -O-CO-R 5 , -O-CO-O-Re, -CO-NH 2 , -CO-NHR 7 , -CO-N(R 7 )(R 8 ), CN, NH 2 , NHR 7 , - N(R 7 )(R 8 ), -NH-CO-R 5 , phenoxy, phen
  • RA is d-C ⁇ 8 alkyl; C 3 -C ⁇ 8 alkenyl; phenyl; C 7 -Cn-phenylalkyl; C 5 -d 2 cycloalkyl; or C 3 -C 50 alkyl, which is interrupted by one to several -O-, -NH-, -NR 7 -, -S- groups, and which can be substituted by OH, phenoxy or C 7 -Ci8alkylphenoxy; or C 2 -C ⁇ 2 -Hydroxyalkyl
  • R 5 is H; d-C ⁇ 8 alkyl; C ⁇ -C ⁇ 8 alkyl substituted with COOH or COOR.; C 2 -d 8 aIkenyl; C 2 - C ⁇ 8 alkenyl substituted with COOH or COOR 4 ; C 5 -C ⁇ 2 cycloalkyl; phenyl; C 7 -Cn-phenylalkyl; C 7 -Cn-alkylphenyl; C 6 -C ⁇ 5 bicycloalkyl; C 6 -C ⁇ 5 bicycloalkenyl; C 6 -C ⁇ 5 tricycloalkyl;
  • R 6 is H; d-d ⁇ alkyl; C 3 -C ⁇ 8 alkenyl; phenyl; C 7 -Cn-phenylalkyl; C 5 -C ⁇ 2 cycloalkyl;
  • R 7 and R 8 are independently phenyl; C ⁇ -C ⁇ 2 alkyl; C 7 -C 13 alkylaryl; C -C 3 aralkyl; C 3 - C ⁇ 2 alkoxyalkyl; C 4 -d 6 -dialkylaminoalkyl; or C 5 -C ⁇ 2 cycloalkyl; or together form a C 3 -C 8 alkylene which may be interrupted by oxygen, sulfur and nitrogen atoms, and or substituted by OH, C 6 -C ⁇ o aryl.
  • Rg is CrC ⁇ 8 alkyl; C 2 -C ⁇ 8 alkenyl; phenyl; C 5 -C ⁇ 2 cycloalkyl; C 7 -Cn-phenylalkyl; C 6 - C ⁇ 5 bicycloalkyl, C 6 -C ⁇ 5 bicycloalkyl-alkyl, C 6 -C ⁇ 5 bicycloalkenyl, or C 6 -C ⁇ 5 tricycIoalkyl;
  • R 10 is C Ci 2 alkyl; phenyl; Naphtyl or C 7 -d 4 alkylphenyl;
  • R 11 is d-Ci 8 alkyl; C 3 -C 6 alkenyl; C 5 -d 2 cycloalkyl; phenyl; naphthyl; biphenylyl; C 7 -Cn- phenylalkyl; C 7 -d alkylphenyl; halogen; C C ⁇ 8 alkoxy;
  • R 3 o, R 31 are independently C -C 12 alkyl; phenyl; or together form a C 3 -C 9 alkylene which may be interrupted by oxygen, sulfur and nitrogen atoms, and or substituted by OH, C 6 -C ⁇ 0 aryl.
  • R55 are independently from each other H; C 6 -C ⁇ 8 aryl; C 6 -d 8 aryl which is substituted by C Ci 8 alkyl, C ⁇ -C ⁇ 8 alkoxy; C C ⁇ 8 alkyl; C ⁇ -C ⁇ 8 alkyl which is interrupted by -0-.
  • R 2 , R 3 are independently from each other, hydrogen, C ⁇ -C 2 oalkyl, C 2 -C ⁇ 8 alkenyl; C 6 -C 14 aryl; C 4 -C 12 cycloalkyl, C 7 -C ⁇ 3 aralkyl, C 7 -C ⁇ 3 alkylaryl; C 1 -C 18 alkyl substituted with phenyl, vinylphenyl, OH, d-C ⁇ 8 alkoxy, C 5 -C ⁇ 2 cycloalkoxy, C 3 -C ⁇ 8 alkenyloxy, halogen, -COOH, - COOR 4 , -O-CO-R 5 , -O-CO-O-Re, -CO-NH 2 , -CO-NHR7, -CO-N(R 7 )(R 8 ), CN, NH 2 , NHR 7 , - N(R 7 )(R 8 ), -NH-CO-R 5 , phenoxy,
  • R 4 is C ⁇ -C ⁇ 8 alkyl; C 3 -C ⁇ 8 alkenyl; phenyl; C 7 -Cn-phenylalkyl; C 5 -C ⁇ 2 cycloalkyl; or C 3 -C 50 alkyl, which is interrupted by one to several -O-, -NH-, -NR 7 -, -S- groups, and which can be substituted by OH, phenoxy or C 7 -C 18 alkylphenoxy; or C 2 -C ⁇ 2 -Hydroxyalkyl
  • R 5 is H; Ci-Cisalkyl; C ⁇ -C 18 alkyl substituted with COOH or COOR 4 ; C 2 -d 8 alkenyl; C 2 - C ⁇ 8 alkenyl substituted with COOH or COORi; C 5 -C ⁇ 2 cycloalkyl; phenyl; C -Cn-phenylalkyl; C 7 -Cn-alkylphenyl
  • R 6 is H; C -C ⁇ 8 alkyl; C -C ⁇ 8 alkenyl; phenyl; C 7 -Cn-phenylalkyl; C 5 -C ⁇ 2 cycloalkyl;
  • R 7 and R 8 are independently phenyl; C ⁇ -C ⁇ 2 alkyl; C 7 -C 13 alkylaryl; C 7 -C 13 aralkyl; C 3 - C ⁇ 2 alkoxyalkyl; C 4 -C 6 -dialkylaminoalkyl; or C 5 -C ⁇ 2 cycloalkyl; or together form a C 3 -C 9 alkylene which may be interrupted by oxygen, sulfur and nitrogen atoms, and or substituted by OH, C 6 -C ⁇ o aryl.
  • Rg is C ⁇ -d 8 alkyl; C 2 -C ⁇ 8 alkenyl; phenyl; C 5 -d 2 cycloalkyl; C 7 -Cn-phenylalkyl; C 6 - C ⁇ 5 bicycloalkyl, C 6 -C ⁇ 5 bicycloalkyl-alkyl, C 6 -C ⁇ 5 bicycloalkenyl, or C 6 -C ⁇ 5 tricycloalkyl;
  • R 10 is C C ⁇ 2 alkyl; phenyl; Naphtyl or C 7 -d alkylphenyl;
  • R 11 is C ⁇ -C 8 alkyl; C 3 -C 6 alkenyl; C 5 -C ⁇ 2 cycloalkyl; phenyl; naphthyl; biphenylyl; C 7 -Cn- phenylalkyl; C 7 -C ⁇ 4 alkylphenyl; halogen; d-C ⁇ 8 alkoxy;
  • R 3 1 are independently C ⁇ -C ⁇ 2 alkyl; phenyl; or together form a C 3 -Cg alkylene which may be interrupted by oxygen, sulfur and nitrogen atoms, and or substituted by OH, C 6 -C . aryl.
  • R 54 , R 55 are independently from each other H; C 6 -C ⁇ 8 aryl; C 6 -C ⁇ 8 aryl which is substituted by C Ci 8 alkyl, C ⁇ -C ⁇ 8 alkoxy; C1-C1 8 alkyl; C ⁇ -C ⁇ 8 alkyl which is interrupted by -O-.
  • R 2 , R 3 are independently from each other, hydrogen, C ⁇ -C 2 oalky
  • R 4 is C C 8 alkyl; phenyl; C 7 -C ⁇ 3 aralkyl, C 7 -C ⁇ 3 alkylaryl
  • R 5 is d-C 8 alkyl; phenyl; C 7 -C ⁇ 3 aralkyl, C 7 -C ⁇ 3 alkylaryl
  • R 6 is linear or branched Ci-Cisalkyl; C 7 -Cn-phenylalkyl; C 5 -C 12 cycloalkyl
  • R7 and R 8 are independently phenyl; d-C ⁇ 2 alkyl; C 7 -C ⁇ 3 alkylaryl; C 7 -C ⁇ 3 aralkyl; C 3 - C ⁇ 2 alkoxyalkyl; C 4 -C ⁇ 6 -dialkylaminoalkyl; or C 5 -C ⁇ 2 cycloalkyl; or together form a C 3 -C 9 alkylene which may be interrupted by oxygen, sulfur and nitrogen atoms, and or substituted by OH, C 6 -do aryl;
  • R 10 is d-C ⁇ 2 alkyl; phenyl; naphtyl or C 7 -C ⁇ 4 alkylphenyl;
  • R 11 is C ⁇ -C ⁇ 8 alkyl; C 3 -C 6 alkenyl; C 5 -C ⁇ 2 cycloalkyl; phenyl; naphthyl; biphenylyl; C 7 -Cn- phenylalkyl; C 7 -d 4 alkylphenyl; halogen; C r C ⁇ 8 alkoxy;
  • R3o, R3 1 are independently C 1 -C 12 alkyl; phenyl; or together form a C 3 -C 9 alkylene which may be interrupted by oxygen, sulfur and nitrogen atoms, and or substituted by OH, C 6 -C ⁇ 0 aryl.
  • R 2 , R 3 are independently from each other, hydrogen, C -C 2 oalkyl, C 2 -C ⁇ 8 alkenyl; C 6 -C ⁇ aryl;
  • R is d-C 8 alkyl; phenyl; C 7 -d 3 aralkyl, C 7 -C ⁇ 3 alkylaryl
  • R 5 is d-C 8 alkyl; phenyl; C 7 -C 3 aralkyl, C 7 -d 3 alkylaryl
  • R 6 is linear or branched C C ⁇ 8 alkyl; C 7 -Cn-phenylalkyl; C 5 -C ⁇ 2 cycloalkyl
  • R 7 and R 8 are independently phenyl; d-C ⁇ 2 alkyl; C 7 -C ⁇ 3 alkylaryl; C 7 -C 13 aralkyl; C 3 - C ⁇ 2 alkoxyalkyl; C 4 -C ⁇ 6 -dialkylaminoalkyl; or C 5 -Ci 2 cycIoalkyl; or together form a C 3 -C 9 alkylene which may be interrupted by oxygen, sulfur and nitrogen atoms, and or substituted by OH, C 6 -C ⁇ o aryl.
  • R 10 is d-C ⁇ 2 alkyl; phenyl; naphtyl or C 7 -C ⁇ 4 alkylphenyl;
  • R 11 is C ⁇ -C ⁇ 8 alkyl; C 3 -C 6 alkenyl; C 5 -C ⁇ 2 cycloalkyl; phenyl; naphthyl; biphenylyl; C 7 -Cn- phenylalkyl; C 7 -d 4 alkylphenyl; halogen; d-C ⁇ 8 alkoxy;
  • R 30 , R 31 are independently C 1 -C 12 alkyl; phenyl; or together form a C 3 -C 9 alkylene which may be interrupted by oxygen, sulfur and nitrogen atoms, and or substituted by OH, C 6 -C ⁇ 0 aryl. Further examples are of the formula Im
  • R 2 , R 3 are independently from each other, hydrogen, C ⁇ -C 20 alkyl, C 2 -C ⁇ 8 alkenyl; C 6 -C ⁇ 4 aryl;
  • R 4 is C ⁇ -C 8 alkyl; phenyl; C 7 -C ⁇ 3 aralkyl, C 7 -d 3 alkylaryl;
  • R 5 is C C 8 alkyl; phenyl; C -C ⁇ 3 aralkyl, C 7 -C 3 alkylaryl;
  • R 6 is linear or branched C ⁇ -C ⁇ 8 alkyl; C 7 -C ⁇ phenylalkyl; C 5 -d 2 cycloalkyI;
  • R 7 and R 8 are independently phenyl; d-C 12 alkyl; C 7 -C 13 alkylaryl; C 7 -d 3 aralkyl; C 3 - C ⁇ 2 alkoxyalkyl; C 4 -C ⁇ 6 -dialkylaminoalkyl; or C 5 -d 2 cycloalkyl; or together form a C 3 -C 9 alkylene which may be interrupted by oxygen, sulfur and nitrogen atoms, and or substituted by OH, C 6 -C o aryl;
  • R 10 is C C ⁇ 2 alkyl; phenyl; naphthyl or C 7 -d 4 alkylphenyl;
  • R 11 is d-C ⁇ 8 alkyl; C 3 -C 6 alkenyl; C 5 -C ⁇ 2 cycloalkyl; phenyl; naphthyl; biphenylyl; C7-G 11 - phenylalkyl; C 7 -d alkylphenyl; halogen; C C ⁇ 8 alkoxy; 3o > R31 are independently C1-C12 alkyl; phenyl; or together form a C 3 -C 8 alkylene which may be interrupted by oxygen, sulfur and nitrogen atoms, and or substituted by OH, C 6 -C ⁇ 0 aryl.
  • R 2 , R 3 are independently from each other, hydrogen, C ⁇ -C 2 _alkyl, C 2 -C ⁇ 8 alkenyl; C 6 -C ⁇ 4 aryl;
  • Rt is d-C 8 alkyl; phenyl; C 7 -C ⁇ 3 aralkyl, C 7 -Ci 3 alkylaryl;
  • R 5 is d-C 8 alkyl; phenyl; C 7 -Ci 3 aralkyl, C 7 -C ⁇ 3 alkylaryl;
  • R 6 is linear or branched C ⁇ -d 8 alkyl; C 7 -Cn-phenylalkyl; C 5 -C ⁇ 2 cycloalkyl;
  • R 7 and R 8 are independently phenyl; d-d 2 alkyl; C7-C1 3 alkylaryl; C7-C1 3 aralkyl; C 3 - C ⁇ 2 alkoxyalkyl; C 4 -C ⁇ 6 -dialkylaminoalkyl; or C 5 -C ⁇ 2 cycloalkyl; or together form a C 3 -C 9 alkylene which may be interrupted by oxygen, sulfur and nitrogen atoms, and or substituted by OH, C 6 -C ⁇ o aryl;
  • R 10 is C C ⁇ 2 alkyl; phenyl; naphtyl or C 7 -d 4 aIkylphenyl; R1 1 is C ⁇ -C ⁇ 8 alkyl; C 3 -C 6 alkenyl; C 5 -C ⁇ 2 cycloalkyl; phenyl; naphthyl; biphenylyl; C 7 -Cn- phenylalkyl; C 7 -C ⁇ 4 alkylphenyl; halogen; d-C ⁇ 8 alkoxy;
  • R31 are independently C1-C12 alkyl; phenyl; or together form a C 3 -Cg alkylene which may be interrupted by oxygen, sulfur and nitrogen atoms, and or substituted by OH, C 6 -C ⁇ 0 aryl;
  • R 13 is d-Ce-alkoxy; C C 8 -alkyl; NR 2 R 3 .
  • any alkyl within the range defined embraces, for example, branched or unbranched alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, 2-ethyIbutyl, n-pentyl, isopentyl, 1 -methyl pentyl, 1,3-dimethyl butyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1- methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethyl hexyl, 1,1,3,3-tetramethylpenty], nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,
  • Alkyl interrupted by more than one O is, for example, polyoxyalkylene such as a polyethylene glycol residue.
  • alkenyl comprises, inter alia, vinyl, allyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct- 2-enyl, n-dodec-2-enyl, iso-dodecenyl, n-dodec-2-enyl, n-octadec-4-enyI.
  • Halogen is mainly fluoro, chloro, bromo or iodo, especially chloro.
  • cycloalkyl mainly is cyclopentyl, cyclohexyl, cyclododecyl; especially cyclohexyl.
  • Aryl usually means C 6 -C ⁇ 2 aryl, preferably phenyl or naphthyl, especially phenyl.
  • Aralkyl is usually the alkyl as defined, which is substituted by the above aryl; preferred is C 7 - Cnphenylalkyl.
  • Alk(yl)aryl is the above aryl substituted by alkyl; preferred is phenyl mono-, di- or trisubstituted by d-C 4 alkyl.
  • Groups which may be unsubstituted or substituted by selected radicals such as C 6 -d 2 aryl or C 5 -Ci2cycloalkyl, like a phenyl or a cyclohexyl ring, are preferably unsubstituted or mono-, di- or tri-substituted, especially preferred are these groups unsubstituted or mono- or disubstituted.
  • the instant compounds of formula I are especially notable for their high UV absorbance, good photostability and excellent compatibility with organic substrates.
  • novel triazine compounds of the formula I are especially efficient as UV absorbers; they are thus useful as stabilizers for a wide variety of organic materials, e.g. thermoplastic polymers, recording materials and coating materials, against damage thereto by light, and as light stabilizers for textile fibre materials and colourings thereof. They may further be used in cosmetic preparations, especially as UV absorbers in sunscreens and preparations for hair treatment such as shampoos, conditioners etc.
  • the materials to be stabilized can, for example, be oils, fats, waxes, coating materials, cosmetics, photographic materials or biocides. Of particular interest is their use in polymeric materials as are present in plastics, rubbers, coating materials, photographic materials or adhesives. When used in cosmetic preparations, the material to be protected is frequently not the preparation itself but skin or hair or hair colouring to which the preparation is applied.
  • the compounds of the present invention are (due to their significantly red shifted absorbance) particularly suitable for the protection of substrates which are sensitive towards longer wavelengths, i.e. above 350 nm into the near visible (400- 420 nm).
  • Examples include coatings (substrates) based on resins containing aromatic moieties (e.g. aromatic epoxy resins) such as cathodic electrocoats.
  • Polymers of monoolefins and diolefins for example polypropylene, polyisobutylene, po- lybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbomene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
  • HDPE high density polyethylene
  • HDPE-HMW high density and high molecular weight polyethylene
  • HDPE-UHMW high density and ultrahigh molecular weight polyethylene
  • MDPE medium density polyethylene
  • Polyolefins i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
  • a catalyst that normally contains one or more than one metal of groups IVb, Vb, Vlb or VIII of the Periodic Table.
  • These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either ⁇ - or ⁇ -coordinated.
  • These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide.
  • These catalysts may be soluble or insoluble in the polymerisation medium.
  • the catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups la, lla and/or Ilia of the Periodic Table.
  • the activators may be modified conveniently with further ester, ether, amine or silyl ether groups.
  • These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
  • Copolymers of monoolefins and diolefins with each other or with other vinyl monomers for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copo- lymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers (e.g.
  • ethylene/norbomene like COC ethylene/1 -olefins copolymers, where the 1-olefin is generated in-situ; propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/vi- ⁇ ylcyclohexene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethyl idene-norbomene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethy- lene-propylene copolymers, LD
  • Hydrocarbon resins for example C 5 -C 9
  • hydrogenated modifications thereof e.g. tackifiers
  • mixtures of polyalkylenes and starch
  • Homopolymers and copolymers from 1.) - 4.) may have any stereostructure including syndio- tactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
  • Polystyrene poly(p-methylstyrene), poly( ⁇ -methylstyrene).
  • Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
  • Copolymers including aforementioned vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene/bu- tadiene, styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/pro- pylene/diene terpolymer; and block copo
  • Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6. especially including polycyclohexylethylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).
  • PCHE polycyclohexylethylene
  • PVCH polyvinylcyclohexane
  • Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
  • Graft copolymers of vinyl aromatic monomers such as styrene or ⁇ -methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acry- lonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpoly
  • Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo- chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinyl idene fluoride, as well as copolymers thereof such as vinyl chloride/vinyl idene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
  • halogen-containing vinyl compounds for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinyl idene fluoride, as well as copolymers
  • Polymers derived from ⁇ , ⁇ -unsaturated acids and derivatives thereof such as polyacry- lates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacryloni- triles, impact-modified with butyl acrylate.
  • Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers for example acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/ alkyl methacrylate/butadiene terpolymers.
  • Polymers derived from unsaturated alcohols and amines or the acyl derivatives or ace- tals thereof for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.
  • Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
  • Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11 , polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly- m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetram
  • Polyureas Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.
  • Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
  • Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.
  • Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
  • Blends of the aforementioned polymers for example PP/EPDM, Poly- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
  • polyblends for example PP/EPDM, Poly- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM
  • the invention therefore additionally provides a composition
  • a composition comprising A) an organic material which is sensitive to oxidative, thermal and/or actinic breakdown/buildup and B) as stabilizer at least one compound of the formula I, and also provides for the use of compounds of the formula I stabilizing organic material against oxidative, thermal or actinic brea kdown/bu ild u p .
  • the invention likewise embraces a method of stabilizing organic material against thermal, oxidative and/or actinic breakdown/buildup, which comprises applying or adding at least one compound of the formula I to this material.
  • the amount of stabilizer to be used depends on the organic material to be stabilized and on the intended use of the stabilized material.
  • the novel composition contains from 0.01 to 15, especially from 0.01 to 10 and, in particular, from 0.05 to 5 parts by weight of the stabilizer (component B) per 100 parts by weight of component A).
  • the stabilizer (component B) can be an individual compound of the formula I or else a mixture.
  • novel compositions may comprise as additional component (C) one or more customary additives such as antioxidants, phosphites and phosphonites, further processing stabilizers, fillers, clarifiers, modifiers, acid scavengers, flame retardants and, especially, further light stabilizers.
  • additional component (C) one or more customary additives such as antioxidants, phosphites and phosphonites, further processing stabilizers, fillers, clarifiers, modifiers, acid scavengers, flame retardants and, especially, further light stabilizers.
  • Al Mated mo no phenols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di- methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-bu- tyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-( ⁇ -methylcycIohexyl)-4,6-dimethyl- phenol, 2,6-dioctadecyl-4-methyIphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-meth- oxymethylphenol, nonylphenols which are linear or branched in the side chains, for example 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1
  • Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctyl- thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4- nonylphenol.
  • Hydroquinones and alkylated hvdroquinones for example 2,6-di-tert-butyl-4-methoxy- phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade- cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-bu- tyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hy- droxyphenyl) adipate.
  • 2,6-di-tert-butyl-4-methoxy- phenol 2,5-di-tert-butylhydroquinone, 2,5-di-ter
  • Tocopherols for example ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (vitamin E).
  • Hydroxylated thiodiphenyl ethers for example 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4 , -thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyI-2- methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)- disulfide.
  • Alkylidenebisphenols for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'- methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-( ⁇ -methylcycIohexyl)- phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4- methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butyl- phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methyIenebis[6-( ⁇ -methylben- zyl)-4-nonylphenol], 2,2'-methylenebis[6-( ⁇ -methyl
  • O-, N- and S-benzyl compounds for example 3,5,3',5'-tetra-tert-butyl-4,4 , -dihydroxydi- benzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy- 3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4- tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxy- benzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
  • Hydroxybenzylated malonates for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy- droxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di- d ⁇ decylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1 , 1 ,3,3-te- tramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
  • Aromatic hydroxybenzyl compounds for example 1,3,5-tris(3,5-di-tert-butyl-4-hydroxy- benzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyI-4-hydroxyben__yl)-2,3,5,6-tetrame- thyl benzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
  • Triazine compounds for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy- ani!ino)-1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1 ,3,5-tri- azine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,3,5-triazine, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,2,3-triazine, 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxyben- zyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyan
  • Benzylphosphonates for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphospho- nate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hy- droxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
  • Acylaminophenols for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
  • esters of ⁇ -(3,5-di-tert-butyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9- nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy- lene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyI)isocyanurate, N,N'-bis(hy- droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phos
  • esters of ⁇ -(5-tert-butyl-4-hvdroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis- (hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trione
  • esters of ⁇ -(3,5-dicvclohexyl-4-hvdroxyphenv0propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]
  • esters of 3,5-di-tert-butyl-4-hvdroxyphenyl acetic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]oct
  • Aminic antioxidants for example N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-bu- tyl-p-phenylenediamine, N,N'-bis(1 ,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1 -ethyl-3- methylpenty -p-phenylenediamine, N,N'-bis(1 -methylheptyl)-p-phenylenediamine, N,N'-dicy- clohexyl-p-phenylenediamine, N.N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p- phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1 ,3-dimethylbuty
  • 2-(2'-Hvdroxyphenv0benzotriazoles for example 2-(2'-hydroxy-5'-methylphenyl)benzo- triazole, 2-(3',5'-di-tert-butyl-2 , -hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphe- nyl)benzotriazole, 2-(2'-hydroxy-5'-(1 ,1 ,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di- tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphe- nyl)-5-chlorobenzotriazole, 2-(3 , -sec-butyl-5'-tert-butyl-2 , -hydroxyphenyl)benzotriazole
  • azol-2-ylphenyl 2-[2'-hydroxy-3 , -( ⁇ , ⁇ -dimethylbenzyl)-5'-(1 ,1 ,3,3-tetramethylbutyl)phenyl]- benzotriazole; 2-[2'-hydroxy-3'-(1 ,1 ,3,3-tetramethylbutyl)-5'-( ⁇ , ⁇ -dimethylbenzyl)phenyl]ben- zotriazole.
  • 2-Hvdroxybenzophenones for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyl- oxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
  • Esters of substituted and unsubstituted benzoic acids for example 4 -tert-butyl phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4 -tert-butyl benzoyl )resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzo- ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxyben- zoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
  • Acrylates for example ethyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, isooctyl ⁇ -cyano- ⁇ , ⁇ -diphe- nylacrylate, methyl ⁇ -carbomethoxycinnamate, methyl ⁇ -cyano- ⁇ -methyl-p-methoxycinna- mate, butyl ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate, methyl ⁇ -carbomethoxy-p-methoxycin- namate and N-( ⁇ -carbomethoxy- ⁇ -cyanovinyl)-2-methyIindoline.
  • Nickel compounds for example nickel complexes of 2,2'-thiobis[4-(1,1,3,3-tetramethyl- butyl)phenol], such as the 1 :1 or 1 :2 complex, with or without additional ligands such as n- butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert- butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphe- nylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
  • additional ligands such as n- butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel di
  • Sterically hindered amines for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1 -octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1 ,2,2,6,6-pentamethyl-4-piperi- dyl) n-butyI-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl)- 2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-oc
  • Oxamides for example 4,4'-dioctyloxyoxaniIide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy- 5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
  • Metal deactivators for example N,N'-diphenyloxamide, N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyl- oyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyI dihydrazide.
  • Phosphites and phosphonites for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2 J 4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di- cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol dip
  • Tris(2,4-di-tert-butylphenyl) phosphite (lrgafos ® 168, Ciba-Geigy), tris(nonyl phenyl) phosphite,
  • Hydroxylamines for example NjN-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N- dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N- dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydrox- ylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
  • Nitrones for example N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl- alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone, N- hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-al- pha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta- decylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N
  • Thiosynergists for example dilauryl thiodipropionate or distearyl thiodipropionate.
  • Peroxide scavengers for example esters of ⁇ -thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto- benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis( ⁇ - dodecylmercapto)propionate.
  • esters of ⁇ -thiodipropionic acid for example the lauryl, stearyl, myristyl or tridecyl esters
  • mercaptobenzimidazole or the zinc salt of 2-mercapto- benzimidazole zinc dibutyldithiocarbamate
  • dioctadecyl disulfide pentaerythritol tetrakis( ⁇ - dodecyl
  • Polyamide stabilisers for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
  • Basic co-stabilisers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
  • Basic co-stabilisers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ric
  • Nucleating agents for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers).
  • inorganic substances such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals
  • organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate
  • polymeric compounds such as ionic copolymers (
  • Fillers and reinforcing agents for example calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
  • additives for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
  • the nature and amount of the further stabilizers added are determined by the nature of the substrate to be stabilized and by its intended use. It is common to employ 0.1-10, for example 0.2-5% by weight of a further stabilizer, based on the material to be stabilized. Other additives, for example, fillers, flame retardants etc. may also be used in higher loadings, e.g. up to 50 % by weight, especially up to 30 % by weight of the polymer.
  • the organic materials to be protected are preferably natural, semi-synthetic or synthetic organic materials.
  • the compounds according to the invention can also be used as sun protection agents for human or animal skin or hair.
  • the invention therefore relates also to a cosmetic preparation comprising a UV absorber of formula I, preferably in an amount of from 0.25 to 5 % by weight, based on the total weight of the preparation, and a skin- and hair-tolerable carrier orexcipient.
  • the invention therefore embraces a synergistic stabilizer mixture comprising (a) a compound of the formula I and
  • Preferred sterically hindered amines are, for example, those indicated in the list above under 2.6 or those indicated below as additives to the novel coating compositions.
  • the stabiliser mixtures according to the invention can be used especially advantageously in compositions comprising as component A a synthetic organic polymer, especially a thermoplastic polymer, a binder for coatings, such as, for example, surface-coatings, or a photographic material.
  • Suitable thermoplastic polymers are, for example, polyolefins, especially polyethylene (PE) and polypropylene (PP) and copolymers thereof, and polymers comprising hetero atoms in the main chain (see e.g. US-5288 778, columns 2 and 3).
  • additives according to the invention can be added to the material individually or as a mixture. If desired, the individual components can be mixed with one another before being incorporated into the polymer, for example in a dry state, by compacting or as a melt.
  • incorporación of the additives according to the invention and optionally further components into the polymer is carried out according to customary methods, such as, for example, dry mixing in powder form or wet mixing in the form of solutions, dispersions or suspensions, for example in inert solvents, water or oil.
  • Incorporation of the additives according to the invention and optionally further components can be carried out, for example, before or after shaping, or by applying or adding the dissolved or dispersed additive or additive mixture to the polymer material, with or without subsequent removal of the solvent or suspension agent/dispersant. Addition directly into the processing apparatus (e.g. extruder, mixer etc.), for example from a dry mixture or powder or as a solution or dispersion, suspension or melt, is possible.
  • the incorporation can be carried out in principle in any heatable vessel equipped with stirring apparatus, for example in closed apparatuses, such as kneaders, mixers or stirred vessels. Incorporation is preferably carried out in an extruder or kneader. The incorporation can be carried out under an inert atmosphere or equally in the presence of oxygen.
  • Any conventional apparatus for melting and mixing the polymer can be used for the addition of the additive or additive mixture.
  • Suitable apparatuses such as, for example, those mentioned above, are known in the art.
  • the additives are added during the processing step in the extruder.
  • Especially preferred processing apparatuses are single-screw extruders, twin-screw extruders running in opposite directions or in the same direction, planetary gear extruders or kneaders.
  • Processing machines can be equipped with one or more degassing vessels to which a negative pressure can be applied.
  • Suitable extruders and kneaders are described, for example, in Handbuch der Kunststoffex- trusion, Vol. 1 Gru ⁇ dlagen, editors F. He ⁇ sen, W. Knappe, H. Potente, 1989, pp. 3-7, ISBN: 3-446-14339-4 (Vol. 2 Extrusionsanlag ⁇ n 1986, ISBN 3-446-14329-7).
  • the screw length may, for example, be 1 - 60, preferably 35 - 48, screw diameters.
  • the rotation speed of the screw is preferably 10 - 600 revolutions per minute (rpm), especially 25 - 300 rpm.
  • the maximum throughput depends upon the screw diameter, the rotation speed and the driving force.
  • the process according to the invention can also be operated at less than the maximum throughput by altering the mentioned parameters or by the use of metering machines.
  • the additives according to the invention and optionally further components can be added to the polymer material also by spraying. They are suitable for diluting other additives (for example the above-mentioned conventional additives) or melts thereof, making it possible to spray them on together with the latter. Especially advantageous is addition of the additives according to the invention by spraying during the deactivation of the polymerisation catalyst; in that case, the evolution of vapour can be utilised for deactivation. For example, addition by spraying, optionally together with other additives, can be advantageous in the case of spherically polymerised polyolefins.
  • the additives according to the invention and optionally further additives can be added to the polymer also in the form of concentrates (master batches) that comprise those components, for example, in a concentration of from 1 to 40 %, preferably from 2 to 20 %, relative to the weight of the polymer. That polymer does not necessarily have to have the same structure as the polymer to which the additives are finally added.
  • the polymer may be used in the form of a powder, granules, solutions, suspensions or in the form of latices.
  • Incorporation can be carried out before or during shaping, or by applying the dissolved or dispersed compound to the polymer, where applicable with subsequent evaporation of the solvent.
  • these may also be stabilised in the form of latices.
  • a further possibility of incorporating the compounds of formula I into polymers comprises adding them before, during or immediately after polymerisation of the corresponding monomers or before crosslinking.
  • the compounds of formula I can be added as such or alternatively in encapsulated form (e.g. in waxes, oils or polymers).
  • the stabilised polymer compositions obtained in that manner can be converted into shaped articles, such as e.g.
  • a polymer composition according to the invention having a relatively high content of stabiliser according to the invention is applied in a thin layer (10 - 100 ⁇ m) to a shaped article made from a polymer containing little or no stabiliser of formula I.
  • Application can be carried out simultaneously with the shaping of the basic body, e.g. by so-called coextrusion.
  • Application can also be carried out, however, to the ready-shaped basic body, e.g. by lamination with a film or by coating with a solution.
  • the outer layer or layers of the finished article have the function of a UV filter which protects the interior of the article from UV light.
  • the outer layer contains preferably 5-15 % by weight, especially 5-10 % by weight, of at least one compound of formula I.
  • the UV absorber can also be present in a different layer or in the single polymer layer.
  • the materials stabilised in that manner are distinguished by high resistance to weathering, especially by high resistance to UV light.
  • the polymers retain their mechanical properties and also their colour and gloss for a long time even when used outside.
  • Compounds of the present formula I can be used advantageously in plastics films, for example polyethylene films, of the kind used in agriculture especially as a covering for hothouses.
  • a particular advantage of hothouse films or agrofilms stabilised according to the invention is that it is possible to filter out the portion of UV radiation that directly damages the crops and/or that favours the spread of a number of pathogenic microorganisms, such as fungi and viruses, and pathogenic insects, such as e.g. whitefly, aphids, thrips etc.. Those pests can be significantly reduced if the admission of UV radiation to the plants is prevented or reduced. [R. Reuveni et al., Plasticulture No. 102, p. 7 (1994); Y.
  • the hydroxyphenyl UV absorbers of the present invention exhibit good compatibility and persistence in the polyolefin.
  • the present invention accordingly also contributes to the improvement of agrofilms and describes a method for suppressing microbial infestation of cultivated plants, such as, for example, tomatoes, cucumbers, gourds, melons, citrus fruit, roses, strawberries, grapes, paprika etc..
  • compositions whose component (A) is a film-forming binder for coatings and component (B) is the stabilizer of present invention.
  • the novel coating composition preferably comprises 0.01 - 10 parts by weight of (B), in particular 0.05 - 10 parts by weight of (B), especially 0.1 - 5 parts by weight of (B), per 100 parts by weight of solid binder (A).
  • concentration of the novel stabilizer (component (B)) in the outer layer can be relatively high, for example from 1 to 15 parts by weight of (B), in particular 3 - 10 parts by weight of (B), per 100 parts by weight of solid binder (A).
  • novel stabilizer in coatings is accompanied by the additional advantage that it prevents delamination, i.e. the flaking-off of the coating from the substrate.
  • This advantage is particularly important in the case of metallic substrates, including multilayer systems on metallic substrates.
  • Substrates to be coated include wood, ceramic materials, metals, plastics, or articles coated or stained with organic materials.
  • the binder (component (A)) can in principle be any binder which is customary in industry, for example those described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp. 368-426, VCH, Weinheim 1991. In general, it is a film-forming binder based on a thermoplastic or thermosetting resin, predominantly on a thermosetting resin. Examples thereof are alkyd, acrylic, polyester, phenolic, melamine, epoxy and polyurethane resins and mixtures thereof.
  • Component (A) can be a cold-curable or hot-curable binder; the addition of a curing catalyst may be advantageous.
  • Suitable catalysts which accelerate curing of the binder are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A18, p.469, VCH Verlagsgesellschaft, Weinheim 1991.
  • component (A) is a binder comprising a functional acrylate resin and a crosslinking agent.
  • coating compositions containing specific binders are:
  • polyurethane paints based on aliphatic or aromatic urethanes or polyurethanes and hydroxyl-containing acrylate, polyester or polyether resins;
  • polyurethane paints based on aliphatic or aromatic urethaneacrylates or polyurethaneacryla.es having free amino groups within the urethane structure and melamine resins or polyether resins, if necessary with curing catalyst;
  • thermoplastic polyacrylate paints based on thermoplastic acrylate resins or externally crosslinking acrylate resins in combination with etherified melamine resins;
  • paint systems especially for clearcoats, based on malonate- blocked isocyanates with melamine resins (e.g. hexamethoxymethylmelamine) as crosslinker (acid catalyzed);
  • melamine resins e.g. hexamethoxymethylmelamine
  • UV -curable systems based on oligomeric urethane acrylates and/or acrylatacrylaten, if desired in combination with other oligomers or monomers;
  • Coating systems based on siloxanes are also possible, e.g. systems described in WO 98/56852, WO 98/56853, DE-A-2914427, or DE-A-4338361.
  • the coating composition according to the invention preferably comprises as component (C) a light stabilizer of the sterically hindered amine type, the 2-(2-hydroxyphenyl)-1,3,5-triazine and/or 2-hydroxyphenyl-2H-benzotriazole type, for example as mentioned in the above list in sections 2.1, 2.6 and 2.8.
  • component (C) a light stabilizer of the sterically hindered amine type, the 2-(2-hydroxyphenyl)-1,3,5-triazine and/or 2-hydroxyphenyl-2H-benzotriazole type, for example as mentioned in the above list in sections 2.1, 2.6 and 2.8.
  • light stabilizers of the 2-(2- hydroxyphenyl)-1 ,3,5-triazine type advantageously to be added can be found e.g.
  • the invention therefore also relates to a coating composition which in addition to components (A) and (B) comprises as component (C) a light stabilizer of the sterically hindered amine type.
  • This stabilizer is preferably a 2,2,6,6-tetraalkylpiperidine derivative or a 3,3,5,5-tetraalkyl- morpholin-2-one derivative containing at least one group of the formula
  • G is hydrogen or methyl, especially hydrogen.
  • Component (C) is preferably used in an amount of 0.05 - 5 parts by weight per 100 parts by weight of the solid binder.
  • tetraalkylpiperidine derivatives which can be used as component (C) are given in EP-A-356 677, pages 3 - 17, sections a) to f). These sections of this EP-A are regarded as part of the present description. It is particular expedient to employ the following tetraalkylpiperidine derivatives:
  • the coating composition can also comprise further components, examples being solvents, pigments, dyes, plasticizers, stabilizers, rheologic or thixotropic agents, drying catalysts and/or levelling agents.
  • solvents examples being solvents, pigments, dyes, plasticizers, stabilizers, rheologic or thixotropic agents, drying catalysts and/or levelling agents. Examples of possible components are described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp.429-471, VCH, Weinheim 1991.
  • Possible drying catalysts or curing catalysts are, for example, free (organic) acids or bases, or (organic) blocked acids or bases which may be deblocked by thermal treatment or irradiation, organometallic compounds, amines, amino-containing resins and/or phosphines.
  • organometallic compounds are metal carboxylates, especially those of the metals Pb, Mn, Co, Zn, Zr or Cu, or metal chelates, especially those of the metals Al, Ti , Zr or Hf, or organometallic compounds such as organotin compounds.
  • metal carboxylates are the stearates of Pb, Mn or Zn, the octoates of Co, Zn or Cu, the naphthenates of Mn and Co or the corresponding linoleates, resinates or tallates.
  • metal chelates are the aluminium, titanium or zirconium chelates of acetylacetone, ethyl acetylacetate, salicylaldehyde, salicylaldoxime, o-hydroxyacetophenone or ethyl trifluoroacetylacetate, and the alkoxides of these metals.
  • organotin compounds are dibutyltin oxide, dibutyltin dilaurate or dibutyltin dioctoate.
  • quaternary ammonium salts for example trimethylbenzylammonium chloride.
  • Amino-containing resins are simultaneously binder and curing catalyst. Examples thereof are amino-containing acrylate copolymers.
  • the curing catalyst used can also be a phosphine, for example triphenylphosphine.
  • the novel coating compositions can also be radiation-curable coating compositions.
  • the binder essentially comprises monomeric or oligomeric compounds containing ethylenically unsaturated bonds (prepolymers), which after application are cured by actinic radiation, i.e. converted into a crosslinked, high molecular weight form.
  • the system is UV-curing, it generally contains at least one photoinitiator as well.
  • the novel stabilizers can also be employed without the addition of sterically hindered amines.
  • the coating compositions according to the invention can be applied to any desired substrates, for example to metal, wood, plastic or ceramic materials. They are preferably used as topcoat in the finishing of automobiles. If the topcoat comprises two layers, of which the lower layer is pigmented and the upper layer is not pigmented, the novel coating composition can be used for either the upper or the lower layer or for both layers, but preferably for the upper layer.
  • the coating compositions according to the invention are particularly suitable for the protedion of substrates which are sensitive towards longer wavelengths, i.e. above 350nm into the near visible (400-420nm). Examples include coatings (substrates) based on resins containing aromatic moieties (e.g. aromatic epoxy resins) such as cathodic electro coats.
  • the present coating systems may be applied with special advantage in direct adhesion to an electro coat, e.g. as a clearcoat, pigmented coat or the 2 layers consisting of pigmented coat and clearcoat on top, where the present UV absorber is present either in the (especially bright coloured) pigmented coat or in the clearcoat (see also EP-A-682680).
  • the coating thus obtained comprising the eledro coat in direct adhesion to the metal substrate, and one or more coating layers in direct adhesion to the electro coat (i.e. without intermediate filler layer), where at least one of these layers contains a compound of the formula I, is another preferred subject of the present invention. Coating systems of this type are especially useful for automobile, train and truck finishes.
  • novel coating compositions can be applied to the substrates by the customary methods, for example by brushing, spraying, pouring, dipping or electrophoresis; see also Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp. 491-500.
  • the coatings can be cured at room temperature or by heating.
  • the coatings are preferably cured at 50 - 150°C, and in the case of powder coatings or coil coatings even at higher temperatures.
  • the coatings obtained in accordance with the invention have excellent resistance to the damaging effects of light, oxygen and heat; particular mention should be made of the good light stability and weathering resistance of the coatings thus obtained, for example paints.
  • the coating compositions can comprise an organic solvent or solvent mixture in which the binder is soluble.
  • the coating composition can otherwise be an aqueous solution or dispersion.
  • the vehicle can also be a mixture of organic solvent and water.
  • the coating composition may be a high-solids paint or can be solvent-free (e.g. a powder coating material). Powder coatings are, for example, those described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., A18, pages 438-444.
  • the powder coating material may also have the form of a powder-slurry (dispersion of the powder preferably in water).
  • the pigments can be inorganic, organic or metallic pigments.
  • the novel coating compositions preferably contain no pigments and are used as a clearcoat.
  • the coating composition as a topcoat for applications in the automobile industry, especially as a pigmented or unpigmented topcoat of the paint finish. Its use for underlying coats, however, is also possible.
  • Addition of the present stabilizer to a pigmented coating may also protect the pigment from damaging effects of UV radiation, especially in the case of liquid crystal pigments.
  • the present stabilizers may also be applied on the substrate using plasma deposition.
  • Methods of obtaining a plasma under vacuum conditions has been widely described in the literature, with inductive or capacitive coupling of electrical energy.
  • Direct (DC) or alternating current (AC) may be used with frequencies ranging from the low kHz to the MHz and even microwave (GHz) range.
  • Preferres substrates are selected from metals, semiconductors, glass, quartz or thermoplastic, crosslinked or structurally crosslinked plastics.
  • Preferred semiconductor is silicon, e.g. in the form of wavers.
  • Metals are preferably aluminum, chromium, steel, vanadium, as used for manufacturing of high precision reflectors such as telescope mirrors or beam reflectors. Especially preferred is aluminum.
  • Primary plasma gas can be, for example, He, Ar, Xe, N 2 , O 2 or air, preferred are inert gases such as He, argon or xenon.
  • inert gases such as He, argon or xenon.
  • the deposition process is not sensitive in respect of gas added or type of energy coupling.
  • Relatively low pressure is important.
  • the pressure ranges from 10 "6 mbarto 10 "2 mbar, especially from 10 "3 to 10 "4 mbar.
  • the material may be deposited on a plasma electrode and evaporated right away.
  • the material to be evaporated is located on a plate or in a crucible which may be heated separately, outside the range of the plasma discharge. Cricible or plate may be on positive or negative eledric potential related to the plasma.
  • the temperature for evaporating the stabilizers is preferably 20°C to 350°C, especially 100°C to 250°C.
  • the layer thickness obtained by plasma deposition is from 10 nm to 1000 nm, more preferably from 50 nm to 500 nm, especially preferred from 100 nm to 300 nm.
  • recording materials are to be understood as being, for example, those described in Research Disclosure 1990, 31429 (pages 474-480) for photographic reproduction and other repro- dudion techniques.
  • Recording materials such as e.g. photographic material and components present therein, are described, for example, in US-6 184 375 from column 34, line 9, to column 63, line 52, or in GB-A-2 343 007 from page 22, last paragraph, to page 106, line 35.
  • the compounds according to the invention of formula I can be used therein analogously to the UV absorbers described in GB-A-2 343 007 from page 97, 3rd paragraph, to page 110, in place of those UV absorbers or in combination therewith, or analogously to the compounds of formula I described in US-6 184 375.
  • the compounds according to the invention can also be used advantageously as UV absorbers in protective coatings, films and foils in liquid crystal displays for protedion against UV radiation and to protect polymer material and other components in the liquid crystal displays against damage by UV light. Examples of such fields of application and materials are to be found inter alia in:
  • JP-A-10-152568 (9.6.1998); JP-A-2000-227509 (8.2.1999); JP-A-2000-227508 (2.8.1999); JP-A-11-258425 (30.11.1998); JP-A-11-258421 (13.3.1998); JP-A-11-242119 (30.11.1998); JP-A- 11-119003 (13.10.1997); JP-A-09-288213 (19.4.1996); JP-A-09-288212 (19.4.1996); JP-A- 08-216316 (14.2.1995); JP-A-08-216324 (14.2.1995); and Chem. Abstr. 131:45869.
  • a preferred type of polymer film in this type of application is based on cycloolefins, for instance of cyclopentene or norbornene, as listed further above under point 1 , line 3, in the list of polymers which can be stabilized.
  • the compounds according to the invention can also be used advantageously in optical recording layers and recording media in which laser radiation, e.g. by short-wave irradiation by means of blue laser diodes (wavelength for example 405 nm), causes a change in the optical characteristics, by means of which digital information can be stored and subsequently retrieved from the storage layer or the storage medium.
  • laser radiation e.g. by short-wave irradiation by means of blue laser diodes (wavelength for example 405 nm)
  • blue laser diodes wavelength for example 405 nm
  • Some of the present compounds and derivatives thereof are especially suitable as a dye for optical recording media operating with a short wavelength, e.g. less than 450 nm such as blue laser light of 400-410 nm, usually 405 nm.
  • present invention further provides an optical recording medium comprising a substrate and a recording layer, said recording layer comprising a compound of the formula X
  • a and A' independently are a residue of one of the formulae II' or IV R 4i - r OR'1
  • R'i is H; C C 2 ⁇ alkyl; C 5 -C ⁇ 2 cycloalkyl; C 3 -C 18 alkenyl; phenyl; CrC ⁇ 8 alkyl which is substituted by phenyl, vinylphenyl, C 5 -C ⁇ 2 cycloaIkyl, OH, CrC ⁇ 8 alkoxy, C 5 -C ⁇ 2 cycloalkoxy, C 3 - C ⁇ 8 alkenyloxy, halogen, -COOH, -COOR,, -O-CO-R 5 , -O-CO-O-R 6 , -CO-NH 2 , -CO-NHR7, - CO-N(R 7 )(R 8 ), CN, NH 2 , NHR 7 , -N(R 7 )(R8), -NH-CO-R5, phenoxy, C C 18 alkyl-phenoxy, phenyl-CrC 4 -alkoxy, C 6 -
  • R' 2 is hydrogen
  • Mec is metal locenyl or metallocenyl methyl; t and R' 4 independently are C C 8 alkyl; C 3 -C ⁇ 8 alkenyl; phenyl; C 7 -Cnphenylalkyl; C 5 - C ⁇ 2 cycloalkyl; C 3 -C 50 alkyl, which is interrupted by -O-, -NH-, -NR 7 -, -S-, and/or can be substituted by OH, phenoxy or C 7 -C 8 alkylphenoxy or Mec; or is C 2 -C ⁇ 2 hydroxyalkyl;
  • R 5 is H; C r C ⁇ 8 alkyl; Mec; C C 18 alkyl substituted by COOH, COOR ⁇ .; C 2 -C 18 alkenyl; C 2 - C 18 alkenyl substituted by COOH or COOR 4 ; C 5 -C 12 cycloalkyl; phenyl; C 7 -C 11 phenylalkyl; C 7 - Cnalkylphenyl; C 6 -C 15 bicycloalkyl; C 6 -C 15 bicycloalkenyl; C 6 -C 15 tricycloalkyl;
  • R 6 is C ⁇ -C ⁇ 8 alkyl; C 3 -C ⁇ 8 alkenyl; phenyl; C 7 -Cnphenylalkyl; C 3 -C ⁇ 2 cycloalkyl;
  • R' 6 is H; C C ⁇ 8 alkyl; C 3 -C 18 alkenyl; phenyl; C 7 -Cnphenylalkyl; C 5 -C ⁇ 2 cycloalkyl;
  • R 7 and R 8 are independently phenyl; C C 12 alkyl; C 7 -C ⁇ 3 aralkyl; C 7 -C ⁇ 3 alkylaryl; C 3 - C ⁇ 2 alkoxyalkyl; C 4 -C 16 dialkylaminoalkyl; or C 5 -C ⁇ 2 cycloalkyl; or together form a C 3 -C 9 alkylene or C 3 -C 9 alkylene which is interrupted by -O-, -NRV, -S- and/or substituted by OH, C 6 -C 10 aryl;
  • R 9 is C r C ⁇ 8 alkyl; C 2 -C 8 alkenyl; phenyl; C 5 -C ⁇ 2 cycloalkyl; C 7 -C 11 phenylalkyl; C B -C 15 - bicycloalkyl, C 6 -C ⁇ 5 bicycloalkyl-alkyl, C 6 -C 15 bicycloalkenyl, or C 7 -C ⁇ 5 tricycloalkyl
  • R 1 0 is C C ⁇ 2 alkyl; phenyl; naphtyl or C 7 -C 14 alkylphenyl;
  • R 11 is H; C ⁇ -C ⁇ 8 alkyl; C 3 -C 6 alkenyl; C 5 -C ⁇ 2 cycloalkyl; phenyl; naphthyl; biphenylyl; C 7 -C 11 - phenylalkyl; C 7 -C ⁇ 4 alkylphenyl; halogen; C C 18 alkoxy;
  • R30, R 31 are independently C C ⁇ 2 alkyl; phenyl; or together, if attached to the same atom, are C 3 -C 9 alkylene or C 3 -C 9 alkylene which is interrupted by -O-, -NH-, -NR 7 -, -S- and/or substituted by OH, C 6 -C ⁇ 0 aryl;
  • R 4 ⁇ is H, C C 18 alkyl; C 5 -C 12 cycIoalkyl; C 2 -C ⁇ 8 alkenyl; phenyl; C 7 -Cnphenylalkyl; C 7 - Cnalkylphenyl; OH; NH 2 ; NHR 7; NR 7 R 8 ; SR1; halogen; COOH, COOR ; -O-CO-R5, -O-CO- OR 6 , CONH 2 ; CONHR7; CONR 7 R 8; COR 9 ; SOz-O ⁇ ; SO 2 R ⁇ 0 ; SORn; NO 2 ;
  • R M is H, C C 18 alkyl; C 5 -C 12 cycloalkyl; C 2 -C 18 alkenyl; phenyl; C 7 -Cnphenylalkyl; C 7 - Cnalkylphenyl; OH; O ® ; NR 7 R 8 ; SR ⁇ halogen; COOH, COOR CONH 2 ; CONHR 7 ; CONR 7 R 8; COR 9 ; SOz-OR* SO 2 R ⁇ 0 ; SO-Rn; NO 2 ;
  • j 5 , R are independently from each other hydrogen; C ⁇ -C ⁇ 8 alkyl; C 4 -C 12 cycloalkyl; C 2 - C ⁇ 8 alkenyl; phenyl; C 7 -Cnphenylalkyl; C 7 -Cnalkylphenyl; -CH 2 CH(OR 5 o)R 5 i; - CH 2 CH(OR 52 )CHOR 50 ;
  • R ⁇ , 1 7 are independently from each other hydrogen; C C ⁇ 8 -alkyl; C -C 2 cycloalkyl; C 2 - C ⁇ 8 alkenyl; phenyl; C 7 -Cnphenylalkyl; C 7 -Cnalkylphenyl; CH 2 CH(OR5o)Rs ⁇ ; CH 2 CH(OR 52 )CHOR 5 o; or R ⁇ , R 4 7 together form a C 3 -C 9 alkylene which may be interrupted by -O-, -NH-, -NR7-, -S- and or substituted by OH, C 6 -C 10 aryl;
  • Rjg is CrC 18 alkyl; C 5 -C 12 cycloalkyl; C 2 -C 18 alkenyl; phenyl; C -Cnphenylalkyl; C 7 - Cnalkylphenyl; -CH 2 CH(OR 5 o)R 5 ⁇ ; -CH 2 CH(OR 52 )CHOR 5 o; -COR 5 ,
  • R OT , R 52 are independently from each other H; CrC ⁇ 8 alkyl; C 3 -C ⁇ 8 alkenyl; C 5 -C ⁇ 2 cycloalkyl; CrC alkyl-cyclohexyl; C 6 -C ⁇ aryl; C 7 -Cnphenylalkyl; C 7 -C ⁇ 4 alkylphenyl;
  • R5 1 is CrCi 8 alkyl; C 2 -C ⁇ 8 alkenyl; C 5 -C ⁇ 2 cycloalkyl; C ⁇ -C alkyl-cyclohexyl; C 6 -C ⁇ aryl; C -Cnphenylalkyl; C 7 -C 14 alkylphenyl; C 6 -C ⁇ 5 bicycloalkyl; C 6 -C 15 bicycloalkenyl; C 6 - C ⁇ 5 tricycloalkyl;
  • R 55 are independently from each other H; C 6 -Ci 8 aryl; C 6 -C ⁇ 8 aryl which is substituted by CrC ⁇ 8 alkyl, C Ci 8 alkoxy; C C ⁇ 8 alkyl; CrC ⁇ 8 alkyl which is interrupted by -O-; and Rse, R 57 and R 58 independently are C 6 -C ⁇ 8 aryl; C 6 -C ⁇ 8 aryl which is substituted by C C ⁇ 8 alkyl, C C 18 alkoxy; d-C 18 alkyl; C 3 -C 18 alkyl which is interrupted by -O-.
  • Mec usually is a transition metal metallocene group bonded directly or over a methylene bridge.
  • Preferred transition metals in Mec are Fe, Ni, Co, especially Fe, as in the groups
  • R'i is most preferably H or alkyl such as CrC ⁇ 2 aIkyl.
  • R 4 is most preferably C C ⁇ 2 alkyl or C 2 -C ⁇ 2 hydroxyalkyl.
  • R 5 is most preferably C C ⁇ 2 alkyl, phenyl or Mec.
  • R 4 ⁇ is most preferably hydrogen.
  • R « is most preferably hydrogen, alkyl or halogen such as F, Cl or especially Br.
  • Preferred are compounds wherein the R ⁇ are mixtures of Cl and Br, either within the same compound or in different compounds.
  • the present invention further relates to an electroluminescent device comprising an anode, a cathode and one or a plurality of organic compound layers sandwiched therebetween, in which said organic compound layers comprise an organic compound containing one ore more compounds of the formula X.
  • the optical information storage material is most preferably a disc recordable for example according to the Blu Ray ® or HD-DVD (Blu Laser") standards (Blu Ray Disc, DV-R. CD-R: 780 nm; DVD-R: 650 nm), preferably a layered construction containing polymer materials such as acrylic resins, styrenic resins, epoxy resins, especially polycarbonate. Thickness of the recording layer containing the compound of the formula X, preferably in a percentage of 30 - 100 % by weight, usually is 1 - 1000 nm, especially 1 - 300 nm.
  • the optical recording materials according to the invention exhibit excellent spectral properties of the solid amorphous recording layer.
  • the absorption band is narrow and intense, having an especially high degree of steepness on the long-wavelength side.
  • the reflectivity of the layers in the region of the writing and reading wavelength is high in the unwritten state.
  • Recording and playback can be carried out at the same wavelength.
  • a simple lens with a single laser source of, advantageously, from 350 to 500 nm, especially up to 480 nm, preferably from 370 to 450 nm, is therefore used.
  • the wavelength is especially preferably in the UV range from 370 to 390 nm, especially approximately 380 nm, or especially at the margin of the visible range from 390 to 430 nm, especially approximately 405 ⁇ 5 nm.
  • UV-VCSELs Very-Cavity Surface-Emitting Laser
  • a laser source already exists as a prototype [Jung Han etal., cf. MRS Internet J. Nitride Semicond. Res. 5S1 , W6.2 (2000)].
  • wavelengths of from 350 to 500 nm by means of conversion of the second harmonic oscillation of a laser source of higher wavelength, for example a laser source of a wavelength of from 700 to 1000 nm.
  • the invention accordingly relates also to a method for the recording or playback of data that comprises recording or playing back the data at a wavelength of from 350 to 500 nm on an optical recording medium according to the invention.
  • the recording medium is based on the structure of known recording media and may, for example, be construded from a transparent substrate; a recording layer comprising at least one of the compounds of formula (X); a reflector layer; and a covering layer, the writing and reading being carried out through the substrate.
  • Suitable substrates include, for example, glasses, minerals, ceramics and thermosetting or thermoplastic plastics.
  • Preferred supports are glasses and homo- or co-polymeric plastics.
  • Suitable plastics include, for example, thermoplastic polycarbonates, polyamides, polyesters, polyacrylates and polymethacrylates, polyurethanes, polyolefins, polyvinyl chloride, poly- vinylidene fluoride, polyimides, thermosetting polyesters and epoxy resins. Special preference is given to polycarbonate substrates, which can be produced, for example, by means of injection-moulding.
  • the substrate may be in pure form or may also comprise customary additives, for example UV absorbers or dyes, as proposed, for example, in JP-A-04/167239 as light stabilisation for the recording layer.
  • the dye added to the supporting substrate exhibits no absorption or at most a small amount of absorption in the range of the writing wavelength (emission wavelength of the laser), preferably up to a maximum of approximately 20 % of the laser light focussed onto the recording layer.
  • the substrate is transparent over at least a portion of the range from 350 to 500 nm, so that it is permeable to, for example, at least 80 % of the light of the writing or reading wavelength incident thereon.
  • the substrate advantageously has a thickness of from 10 ⁇ m to 2 mm, especially from 100 to 1200 ⁇ m, more especially from 600 to 1100 ⁇ m, with a preferably spiral -shaped guide groove (track) on the coating side, a groove depth of from 10 to 200 nm, preferably from 80 to 150 nm, a groove width of from 100 to 400 nm, preferably from 150 to 250 nm, and a spacing between 2 revolutions of from 200 to 600 nm, preferably from 350 to 450 nm.
  • Grooves of various cross-sectional profiles are known, for example rectangular, trapezium-shaped or V-shaped.
  • the guide groove may, in addition, undergo a small periodic or quasi-periodic lateral deflection ("wobble"), allowing synchronisation of the speed of rotation and absolute positioning of the reading head ("pick-up").
  • the same function can be performed, instead of or in addition to the deflection, by markings between adjacent grooves ("pre-pits").
  • the recording composition is applied, for example, by spin-coating a solution, the intention being to provide a layer that is as amorphous as possible, the thickness of which on the surface ("land") is advantageously from 0 to 40 nm, especially from 1 to 20 nm, more especially from 2 to 10 nm, and the thickness of which in the groove, depending on the groove geometry, is advantageously from 20 to 150 nm, especially from 50 to 120 nm, more especially from 60 to 100 nm.
  • Suitable reflecting materials for the reflector layer are especially metals that readily reflect the laser radiation used for the recording and playback, for example metals of the third, fourth and fifth main groups and of the sub-groups of the periodic table of chemical elements.
  • the following are especially suitable: Al, In, Sn, Pb, Sb, Bi, Cu, Ag, Au, Zn, Cd, Hg, Sc, Y, La, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Fe, Co, Ni, Ru, Rh, Pd, Os, lr, Pt and the lanthanide metals Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, as well as alloys thereof.
  • the reflector layer has a thickness of, advantageously, from 5 to 200 nm, especially from 10 to 100 nm, more especially from 40 to 60 nm, but thicker reflector layers are also possible, for example 1 ⁇ m thick or even more.
  • Suitable materials for the covering layer are mainly plastics, which are applied in a thin layer to the reflector layer either directly or with the aid of adhesion promoters.
  • mechanically and thermally stable plastics having good surface properties that can still undergo modification, for example writing, are selected.
  • the plastics can be either thermosetting or thermoplastic.
  • coatings that are radiation-cured (for example using UV radiation), which are especially simple and economical to produce.
  • radiation-curable monomers and oligomers include acrylates and methacrylates of diols, triols and tetrols, polyimides of aromatic tetracarboxylic acids and aromatic diamines having d-C 4 alkyl groups in at least two positions ortho to the amino groups, and oligomers having dialkylmaleinimidyl groups, for example dimethylmaleinimidyl groups.
  • the adhesion promoters used are likewise preferably radiation-curable monomers and oligomers.
  • a second substrate comprising recording layer and reflector layer, with the result that the recording medium can be played on both sides. Preference is given to a symmetrical structure in which the two parts are joined to one another, on the reflector side, directly by means of an adhesion promoter, or by way of an intermediate layer.
  • the optical properties perse of the covering layer, or of the covering materials essentially play no part except that curing thereof may, where appropriate, be carried out by means of, for example, UV radiation.
  • the main function of the covering layer is to ensure the mechanical strength of the recording medium as a whole and, if necessary, the mechanical strength of thin reflector layers. Where the recording medium is adequately stable, for example when a thick reflector layer is present, it may even be possible to dispense with the covering layer completely.
  • the thickness of the covering layer depends on the thickness of the recording medium as a whole, which should preferably be a maximum of approximately 2 mm.
  • the covering layer preferably has a thickness of from 10 ⁇ m to 1 mm.
  • the recording media according to the invention may also have additional layers, for example interference layers or barrier layers. It is also possible for recording media to be constructed with a plurality of (for example from two to ten) recording layers. The structure and the use of such materials are known to the person skilled in the art. Preference is given, where appropriate, to interference layers that are arranged between the recording layer and the refleding layer and/or between the recording layer and the substrate and that consist of a dielectric material, for example, of TiO 2 , Si 3 N 4 , ZnS or silicone resins, as described in EP-A-0 353 393.
  • a dielectric material for example, of TiO 2 , Si 3 N 4 , ZnS or silicone resins
  • the recording media according to the invention can be prepared according to methods known perse, it being possible for various coating methods to be used depending on the materials employed and their mode of operation.
  • Suitable coating methods include, for example, immersion, pouring, brushing, knife coating, and spin-pouring, as well as vapour deposition methods, which are carried out in high vacuum.
  • pouring methods solutions in organic solvents are generally employed.
  • solvents it must be ensured that the supports employed are not sensitive to those solvents.
  • Suitable coating methods and solvents are described, for example, in EP A-0401 791.
  • the recording layer is preferably applied by spin-coating a dye solution
  • solvents that have proved especially suitable being alcohols, for example 2-methoxyethan ⁇ l, isopropanol or n-butanol, hydroxyketones, for example diacetone alcohol or 3-hydroxy-3-methyl-2- butanone, hydroxy esters, for example lactic acid methyl ester or isobutyric acid methyl ester, or preferably fluorinated alcohols, for example 2,2,2-trifluoroethanol or2,2,3,3-tetrafluoro-1- propanol, and mixtures thereof.
  • solvents that have proved especially suitable being alcohols, for example 2-methoxyethan ⁇ l, isopropanol or n-butanol, hydroxyketones, for example diacetone alcohol or 3-hydroxy-3-methyl-2- butanone, hydroxy esters, for example lactic acid methyl ester or isobutyric acid methyl ester, or preferably fluorinated alcohols, for example 2,2,2-tri
  • the metallic refledor layer is preferably applied by atomization (sputtering) or by vapour deposition in vacuo.
  • atomization sputtering
  • vapour deposition in vacuo.
  • the recording is carried out according to known methods by writing pits (marks) of fixed or variable length by means of a modulated, focussed laser beam guided at constant or variable speed over the surface of the recording layer.
  • the information is read according to methods known perse by registering the variation in reflection using laser radiation, for example as described in "CD-Player und R-DAT Recorder” (Claus Biaesch-Wiepke, Vogel Buchverlag, W ⁇ rzburg 1992). The requirements are known to the person skilled in the art.
  • the information-containing medium according to the invention is especially an optical information material of the WORM type. It can be used, for example, analogously to CD-R (compact disc - recordable) or DVD-R (digital video disc - recordable) in computers, and also as storage material for identity cards and security cards or for the manufacture of diffractive optical elements, for example holograms.
  • An inverse layer structure in which the layer sequence is substrate, reflector layer, recording layer and covering layer, is accordingly preferred.
  • the recording layer is thus located between the reflector layer and the covering layer. Recording and playback are therefore carried out not through the substrate, but through the covering layer.
  • the respedive roles of the covering layer and the substrate especially the geometry and the optical properties, are thus reversed.
  • a number of corresponding design arrangements are described in Proceedings SPIE-lnt. Soc. Opt. Eng. 1999, 3864 for digital video recordings in conjunction with a blue GaN laser diode.
  • the recording layer preferably comprises a compound of formula (X) or a mixture of such compounds as the main component, for example at least 20 % by weight, especially at least 50 % by weight, more especially at least 80 % by weight.
  • a compound of formula (X) or a mixture of such compounds as the main component for example at least 20 % by weight, especially at least 50 % by weight, more especially at least 80 % by weight.
  • Further customary constituents are possible, for example other chromophores (for example those having an absorption maximum at from 300 to 1000 nm), stabilisers, free radical capture agents (for example for 1 O 2 ), or luminescence quenchers, melting point reducers, decomposition accelerators, or any other additives that have already been described in optical recording media.
  • such chromophores may in principle be any dyes that can be decomposed or modified by the laser radiation during the recording, or that may be inert towards the laser radiation.
  • the further chromophores are decomposed or modified by the laser radiation, this can take place directly by absorption of the laser radiation or can be induced indirectly by the decomposition of the compounds of formula (X) according to the invention, for example thermally.
  • chromophores or coloured stabilisers may influence the optical properties of the recording layer. It is therefore preferable to use further chromophores or coloured stabilisers, the optical properties of which conform as far as possible to, or are as different as possible from, those of the compounds of formula (X), or the amount of further chromophores is kept small.
  • UV absorbers that are hypsochromic to the dye of formula (X)
  • coloured stabilisers that are bathochromic to the dye of formula (X) and have absorption maxima lying, for example, in the NIR or IR range.
  • Other dyes can also be added for the purpose of colour-coded identification, colour-masking ("diamond dyes") or enhancing the aesthetic appearance of the recording layer.
  • the wavelengths of the inversion points of the further chromophores and of the compounds of formula (X) are a maximum of 40 nm, especially a maximum of 20 nm, apart.
  • the further chromophores and the compounds of formula (X) should exhibit similar behaviour in resped of the laser radiation, so that it is possible to use as further chromophores known recording compositions the adion of which is synergistically enhanced or heightened by the compounds of formula (X).
  • chromophores or coloured stabilisers having optical properties that are as different as possible from those of compounds of formula (X)
  • they advantageously have an absorption maximum that is hypsochromically or bathochromically shifted relative to the dye of formula (X).
  • the absorption maxima are preferably at least 50 nm, especially at least 100 nm, apart.
  • the amount thereof should preferably be small so that their contribution to the total absorption of the recording layer in the range of from 350 to 450 nm is a maximum of 20 %, preferably a maximum of 10 %.
  • the amount of additional dye or stabiliser is advantageously a maximum of 50 % by weight, preferably a maximum of 10 % by weight, based on the recording layer.
  • chromophores that can be used in the recording layer, in addition to the compounds of formula (X), are, for example, cyanines and cyanine metal complexes (US 5958 650), styryl compounds (US-6 103 331), oxonol dyes (EP-A-833 314), azo dyes and azo metal complexes (JP-A-11/028865), phthalocyanines (EP-A-232427, EP-A-337 209, EP-A-373 643, EP-A-463 550, EP-A-492 508, EP-A-509423, EP-A-511 590, EP-A-513 370, EP-A-514 799, EP-A-518 213, EP-A-519 419, EP-A-519 423, EP-A-575 816, EP-A-600 427, EP-A-676 751, EP-A-712 904, WO-98/14520, WO-00/09522, WO 02/083796), por
  • the amount of those chromophores should preferably be so small that the absorption thereof at the wavelength of the inversion point of the longest-wavelength flank of the absorption of the solid layer as a whole is, at the same wavelength, a fraction, advantageously no more than ⁇ , especially no more than 15, more especially no more than /10, of the absorption of the pure compound of formula (X) in the solid layer as a whole.
  • the absorption maximum is preferably higher than 425 nm, especially higher than 500 nm.
  • Stabilisers or luminescence-quenchers are, for example, metal complexes of N- or S- containing enolates, phenolates, bisphenolates, thiolates or bisthiolates or of azo, azomethine or formazan dyes, such as ® lrgalan Bordeaux EL (Ciba Specialty Chemicals Inc.), ® Cibafast N (Ciba Specialty Chemicals Inc.) or similar compounds, hindered phenols and derivatives thereof (optionally also as counter-ions X), such as ® Cibafast AO, o-hydroxy- phenyl-triazoles or -triazines or other UV absorbers, such as ® Cibafast W or ® Cibafast P or hindered amines (TEMPO or HALS, also as nitroxides or NOR-HALS, optionally also as counter-ions X), and also, as cations, diimmonium, ParaquatTM or OrthoquatTM salts,
  • neutral metal complexes for example those disclosed in the publication WO 02/082438 or applications Nos. PCT/EP02/12425 or PCT/EP03/00484 and to which reference is expressly made herein.
  • metal complex additives that may be mentioned are copper complexes, illustrated e.g. by a compound of formula
  • nickel bisphenolates illustrated, for example, by the
  • concentrations of additives are, for example, from 0.001 to 1000 % by weight, preferably from 1 to 50 % by weight, based on the recording agent of formula (X).
  • the invention further pertains to a method of writing or reading digital information in a recording layer by means of laser radiation of wavelength of less than 450 nm, characterized in that the recording layer comprises a compound of the formula X, as well as to the use of a compound of the formula X as a recording dye for optical information storage using laser radiation of less than 450 nm.
  • AH readions are carried out under nitrogen or argon. If not otherwise indicated, all readion mixtures are stirred, percentages are given by weight, and room temperature stands for a temperature in the range 20-25°C. M.p. stands for melting point or range. If not otherwise indicated, compound numbers are identical with numbers of preparation examples.
  • the reaction mixture is hydrolyzed with a mixture of ice and 20 % HCI.
  • the water phase is extracted with dichloromethane.
  • the organic phase is dried over MgSO 4 .
  • the solvent is removed at reduced pressure.
  • the produd is used without purification for the next reaction step (see example 4). Melting point: 112 - 115 °C
  • Example 7 Further derivatization of compound of example 6
  • reaction mixture is then poured on water and extracted with ethylacetate.
  • resulting resinous product is then purified by column chromatography over silica gel with toluene as solvent. 0.53g of an orange oil is obtained; identification by NMR shows the above product besides the corresponding disubstituted product (mono-fluoro: compound 20a) and traces of monosubstituted (bis-fluoro) compound.
  • 0.07g of compound 21 is added together with 0.12g of ferrocenecarboxylic acid, 0.1 Og dicyclocarbodiimide and 0.06g 4-dimethylaminopyridine to 5ml of dichloromethane under nitrogen at room temperature. The mixture is stirred for 7 hours, then washed with a mixture of acetic acid / water and water. The organic solvent is dried and evaporated. The residue is purified by chromatography over silica gel with a 2:1 mixture of toluene/ethylacetate. 0.1 Og of compound 22 is obtained. Infusion APCI-MS shows the molecule peak at 1206.
  • Example 31 Further derivatization of compound of example 6
  • the UV - absorbers of the present invention are incorporated into a thermosetting acryl / melamine clear coat (based on Viacryl® SC 303 / Viacryl® SC 370 / Maprenal® MF 650) in a concentration of 1 % or 2% based on the solids content of the formulation (solids content: 50.4%).
  • Some formulations contain a sterically hindered amine (HALS) as a further stabilizer:
  • HALS sterically hindered amine
  • a further formulation is prepared without stabilizers.
  • the paint is sprayed onto electrocoated aluminium panels (10x30cm) as commercially available from ACT Laboratories (ACT Laboratories, Inc., Southfield, Michigan 48 075, USA) resulting after cure (130°C / 30 min.) in a dry film thickness of 40 ⁇ m.
  • the panels are subsequently exposed in a Xenon - WOM weather-o-meter® (Atlas Corp.) according to SAE J 1960.
  • the adhesion between the clear coat and the light sensitive electrocoat is determined at regular intervals by cross hatch (ISO 2409) followed by tape test.
  • Viacryl SC 303 acrylic resin (Solutia, formerly Vianova Resins)
  • Viacryl SC 370 acrylic resin (Solutia, formerly Vianova Resins)
  • Solvesso 100 aromatic hydrocarbon, bp. 163-180°C (Exxon Corp.)
  • Maprenal MF 650 melamine resin (Solutia, formerly Vianova Resins)
  • Solvesso 150 aromatic hydrocarbon, bp. 180-203 C C (Exxon Corp.)
  • Crystal oil 30 aliphatic hydrocarbon, bp. 145- 200°C (Shell Corp.)
  • the coatings of present invention show good adhesion between clearcoat and electrocoat indicating low transmission of UV light through the clear coat and efficient stabilization of the coating.
  • the recording medium has a reflectivity of 23%.
  • the above compound is vapour-deposited onto a flat glas substrate (thickness 1.2 mm, diameter 120 mm) at a coating rate of 0.3 nm/s in a vacuum vapour deposition apparatus (Balzers) under a high vacuum (1.8 mPa) from a resistance-heated crucible.
  • the refractive index n and the extinction coefficient k of the so-formed layer have been determined by using an optical measurement system (ETA-RT, ETA-Optik).
  • the UV absorbers of the present invention are incorporated into a thermosetting acryl / melamine clear coat (based on Viacryl® SC 303 / Viacryl® SC 370 / Maprenal® MF 650 as listed below) in a concentration of 2% and 3% respectively based on the solids content of the formulation (solids content: 50.4%).
  • a further formulation containing no UV absorber is prepared for comparison purposes.
  • Each sample of the paint is sprayed onto eledro coated aluminium panels (10x30cm) as commercially available from ACT Laboratories (ACT Laboratories, Inc., Southfield, Michigan 48 075, USA) resulting after cure (130°C / 30') in a dry film thickness of 40 ⁇ m.
  • Viacryl SC 303 acrylic resin (Solutia, formerly Vianova Resins)
  • Viacryl SC 370 acrylic resin (Solutia, formerly Vianova Resins)
  • Solvesso 100 aromatic hydrocarbon, bp. 163-180°C (Exxon Corp.)
  • Maprenal MF 650 melamine resin (Solutia, formerly Vianova Resins)
  • Solvesso 150 aromatic hydrocarbon, bp. 180-203°C (Exxon Corp.)
  • Crystal oil 30 aliphatic hydrocarbon, bp. 145- 200°C (Shell Corp.)

Abstract

L'invention concerne un nouveau procédé permettant de préparer des triazines d'aminophényle de formule I', selon lequel est prévu de faire réagir un triazine d'halogénure de phényle de formule I'', avec une amine de formule IX H-NR'2R'3 (IX) dans laquelle X désigne chloro ou de préférence fluoro et les symboles A, A', R'2, R'3 et R44 désignent des restes organiques, comme définis dans la revendication 1. Des produits est de dérivés obtenus à partir dudit procédé s'utilisent comme stabilisants et absorbeurs d'U.V. pour protéger un matériau organique d'éventuelles altérations dues à l'action de la lumière, de l'oxygène et/ou de la chaleur, ou bien comme colorant d'enregistrement dans un support d'enregistrement optique, notamment pour écrire ou lire des informations numériques dans une couche d'enregistrement, par rayonnement laser d'une longueur d'onde inférieure à 450 nm.
PCT/EP2004/050818 2003-05-27 2004-05-17 Triazines d'aminoaryle WO2004106311A2 (fr)

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EP04733351A EP1641768A2 (fr) 2003-05-27 2004-05-17 Aminoaryle-1-3-5 triazine et leur utilization comme absorbeurs d'uv
US10/558,317 US20060252857A1 (en) 2003-05-27 2004-05-17 Aminoaryl-1-3-5-triazines and their use as uv absorbers
JP2006530199A JP2007508275A (ja) 2003-05-27 2004-05-17 アミノアリール−１−３−５トリアジン及びｕｖ吸収剤としてのそれらの使用

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EP03405386 2003-05-27
EP03405386.8 2003-05-27

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EP2160945A1 (fr) 2008-09-09 2010-03-10 Polymers CRC Limited Article antimicrobien
WO2011023584A2 (fr) 2009-08-27 2011-03-03 Polymers Crc Ltd. Composition d'oxyde de zinc-argent de taille nanométrique
WO2011110550A1 (fr) 2010-03-09 2011-09-15 Polymers Crc Ltd Procédé de préparation d'un article antimicrobien
US9034956B2 (en) 2010-11-16 2015-05-19 Basf Se Stabilizer composition for polymers
US20150375178A1 (en) * 2013-06-07 2015-12-31 Lg Chem, Ltd. Polyamide water-treatment separation membrane having superior oxidation resistance and chlorine resistance properties, and method of manufacturing the same
WO2016184766A1 (fr) * 2015-05-18 2016-11-24 Dsm Ip Assets B.V. Nouveau procédé d'éthérification de bis-resorcinyol triazines
EP3418272A1 (fr) * 2017-06-21 2018-12-26 Samsung Display Co., Ltd. Composés triazine et dispositifs électroluminescents organiques les incluant
US11563183B2 (en) 2017-06-21 2023-01-24 Samsung Display Co., Ltd. Heterocyclic compound and organic light-emitting device including the same
US11588111B2 (en) 2017-08-04 2023-02-21 Samsung Display Co., Ltd. Condensed-cyclic compound and organic light-emitting device including the same

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WO2008006744A2 (fr) * 2006-07-14 2008-01-17 Ciba Holding Inc. AGENTS Antimicrobiens À base de polysiloxane
US20080082557A1 (en) * 2006-09-29 2008-04-03 Brother Kogyo Kabushiki Kaisha Business card information management system
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US8802151B2 (en) 2009-03-24 2014-08-12 Basf Se Preparation of shaped metal particles and their uses
JP5719528B2 (ja) * 2009-06-09 2015-05-20 富士フイルム株式会社 新規なトリアジン誘導体、紫外線吸収剤及び樹脂組成物
JP5422269B2 (ja) * 2009-06-23 2014-02-19 富士フイルム株式会社 紫外線吸収剤組成物及び樹脂組成物
JP2015503226A (ja) * 2011-11-15 2015-01-29 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 有機半導体デバイスおよびその製造方法
US9725579B2 (en) * 2014-05-01 2017-08-08 Cytec Industries Inc. Stabilizing compositions for stabilizing materials against ultraviolet light and thermal degradation
CN104591655A (zh) * 2015-01-18 2015-05-06 浙江泰升节能科技有限公司 一种仿真贴面砖材料及其制备方法
TW201718523A (zh) * 2015-06-23 2017-06-01 科思創德意志股份有限公司 作為光起始劑之新型三及其製備
JP7004660B2 (ja) * 2017-04-25 2022-01-21 ビーエーエスエフ ソシエタス・ヨーロピア 紫外線吸収剤に共有結合したコーティング組成物
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EP2160945A1 (fr) 2008-09-09 2010-03-10 Polymers CRC Limited Article antimicrobien
WO2011023584A2 (fr) 2009-08-27 2011-03-03 Polymers Crc Ltd. Composition d'oxyde de zinc-argent de taille nanométrique
WO2011110550A1 (fr) 2010-03-09 2011-09-15 Polymers Crc Ltd Procédé de préparation d'un article antimicrobien
US9034956B2 (en) 2010-11-16 2015-05-19 Basf Se Stabilizer composition for polymers
US9833751B2 (en) * 2013-06-07 2017-12-05 Lg Chem, Ltd. Polyamide water-treatment separation membrane having superior oxidation resistance and chlorine resistance properties, and method of manufacturing the same
US20150375178A1 (en) * 2013-06-07 2015-12-31 Lg Chem, Ltd. Polyamide water-treatment separation membrane having superior oxidation resistance and chlorine resistance properties, and method of manufacturing the same
WO2016184766A1 (fr) * 2015-05-18 2016-11-24 Dsm Ip Assets B.V. Nouveau procédé d'éthérification de bis-resorcinyol triazines
CN107667095A (zh) * 2015-05-18 2018-02-06 帝斯曼知识产权资产管理有限公司 用于醚化双‑间苯二酚基三嗪的新方法
US10179772B2 (en) 2015-05-18 2019-01-15 Dsm Ip Assets B.V. Process for the etherification of bis-resorcinyol triazines
EP3418272A1 (fr) * 2017-06-21 2018-12-26 Samsung Display Co., Ltd. Composés triazine et dispositifs électroluminescents organiques les incluant
US11563183B2 (en) 2017-06-21 2023-01-24 Samsung Display Co., Ltd. Heterocyclic compound and organic light-emitting device including the same
US11844273B2 (en) 2017-06-21 2023-12-12 Samsung Display Co., Ltd. Heterocyclic compound and organic light-emitting device including the same
US11588111B2 (en) 2017-08-04 2023-02-21 Samsung Display Co., Ltd. Condensed-cyclic compound and organic light-emitting device including the same

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US20060252857A1 (en) 2006-11-09
WO2004106311A3 (fr) 2005-01-20
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TW200505877A (en) 2005-02-16
CN1795182A (zh) 2006-06-28
JP2007508275A (ja) 2007-04-05

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